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char = a;code = 97
char = l;code = 108
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char = e;code = 101
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char = a;code = 97
char = c;code = 99
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char = v;code = 118
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char = g;code = 103
char = a;code = 97
char = n;code = 110
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char = m;code = 109
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char = u;code = 117
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char = d;code = 100
char = s;code = 115
char = .;code = 46
result sql = Structural diversity in manganese, iron and cobalt complexes of the ditopic 1,2-bis(2,2'-bipyridyl-6-yl)ethyne ligand and observation of epoxidation and catalase activity of manganese compounds.
Structural diversity in manganese, iron and cobalt complexes of the ditopic 1,2-bis(2,2'-bipyridyl-6-yl)ethyne ligand and observation of epoxidation and catalase activity of manganese compounds.
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char = ;code = 32
char = E;code = 69
char = -;code = 45
char = 1;code = 49
char = ,;code = 44
char = 2;code = 50
char = -;code = 45
char = b;code = 98
char = i;code = 105
char = s;code = 115
char = (;code = 40
char = 2;code = 50
char = ,;code = 44
char = 2;code = 50
char = ';code = 39
char = -;code = 45
char = b;code = 98
char = i;code = 105
char = p;code = 112
char = y;code = 121
char = r;code = 114
char = i;code = 105
char = d;code = 100
char = y;code = 121
char = l;code = 108
char = -;code = 45
char = 6;code = 54
char = -;code = 45
char = y;code = 121
char = l;code = 108
char = );code = 41
char = e;code = 101
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = f;code = 102
char = r;code = 114
char = a;code = 97
char = g;code = 103
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = t;code = 116
char = ;code = 32
char = w;code = 119
char = a;code = 97
char = s;code = 115
char = ;code = 32
char = f;code = 102
char = o;code = 111
char = r;code = 114
char = m;code = 109
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = s;code = 115
char = i;code = 105
char = t;code = 116
char = u;code = 117
char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = L;code = 76
char = ';code = 39
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = b;code = 98
char = r;code = 114
char = i;code = 105
char = d;code = 100
char = g;code = 103
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = b;code = 98
char = e;code = 101
char = t;code = 116
char = w;code = 119
char = e;code = 101
char = e;code = 101
char = n;code = 110
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = w;code = 119
char = o;code = 111
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = ;code = 32
char = c;code = 99
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = s;code = 115
char = ,;code = 44
char = ;code = 32
char = d;code = 100
char = e;code = 101
char = s;code = 115
char = p;code = 112
char = i;code = 105
char = t;code = 116
char = e;code = 101
char = ;code = 32
char = i;code = 105
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = t;code = 116
char = r;code = 114
char = a;code = 97
char = n;code = 110
char = s;code = 115
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = n;code = 110
char = f;code = 102
char = i;code = 105
char = g;code = 103
char = u;code = 117
char = r;code = 114
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ,;code = 44
char = ;code = 32
char = w;code = 119
char = h;code = 104
char = i;code = 105
char = c;code = 99
char = h;code = 104
char = ;code = 32
char = l;code = 108
char = e;code = 101
char = a;code = 97
char = d;code = 100
char = s;code = 115
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = v;code = 118
char = e;code = 101
char = r;code = 114
char = y;code = 121
char = ;code = 32
char = s;code = 115
char = t;code = 116
char = r;code = 114
char = a;code = 97
char = i;code = 105
char = n;code = 110
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = e;code = 101
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = b;code = 98
char = r;code = 114
char = i;code = 105
char = d;code = 100
char = g;code = 103
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = m;code = 109
char = o;code = 111
char = i;code = 105
char = e;code = 101
char = t;code = 116
char = y;code = 121
char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = t;code = 116
char = o;code = 111
char = m;code = 109
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = l;code = 108
char = s;code = 115
char = o;code = 111
char = ;code = 32
char = b;code = 98
char = r;code = 114
char = i;code = 105
char = d;code = 100
char = g;code = 103
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = b;code = 98
char = y;code = 121
char = ;code = 32
char = t;code = 116
char = w;code = 119
char = o;code = 111
char = ;code = 32
char = a;code = 97
char = c;code = 99
char = e;code = 101
char = t;code = 116
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = h;code = 104
char = y;code = 121
char = d;code = 100
char = r;code = 114
char = o;code = 111
char = x;code = 120
char = y;code = 121
char = ;code = 32
char = g;code = 103
char = r;code = 114
char = o;code = 111
char = u;code = 117
char = p;code = 112
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = t;code = 116
char = ;code = 32
char = b;code = 98
char = r;code = 114
char = i;code = 105
char = d;code = 100
char = g;code = 103
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = b;code = 98
char = e;code = 101
char = t;code = 116
char = w;code = 119
char = e;code = 101
char = e;code = 101
char = n;code = 110
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = t;code = 116
char = o;code = 111
char = m;code = 109
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = e;code = 101
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = f;code = 102
char = r;code = 114
char = a;code = 97
char = g;code = 103
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;;code = 59
char = ;code = 32
char = D;code = 68
char = M;code = 77
char = F;code = 70
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = m;code = 109
char = p;code = 112
char = l;code = 108
char = e;code = 101
char = t;code = 116
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = o;code = 111
char = c;code = 99
char = t;code = 116
char = a;code = 97
char = h;code = 104
char = e;code = 101
char = d;code = 100
char = r;code = 114
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = o;code = 111
char = r;code = 114
char = d;code = 100
char = i;code = 105
char = n;code = 110
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = r;code = 114
char = o;code = 111
char = u;code = 117
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = e;code = 101
char = a;code = 97
char = c;code = 99
char = h;code = 104
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = t;code = 116
char = o;code = 111
char = m;code = 109
char = ;code = 32
char = w;code = 119
char = h;code = 104
char = i;code = 105
char = c;code = 99
char = h;code = 104
char = ;code = 32
char = a;code = 97
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = s;code = 115
char = e;code = 101
char = p;code = 112
char = a;code = 97
char = r;code = 114
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = b;code = 98
char = y;code = 121
char = ;code = 32
char = 3;code = 51
char = .;code = 46
char = 3;code = 51
char = 5;code = 53
char = 1;code = 49
char = ;code = 32
char = A;code = 65
char = .;code = 46
char = ;code = 32
char = A;code = 65
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = m;code = 109
char = p;code = 112
char = r;code = 114
char = o;code = 111
char = p;code = 112
char = o;code = 111
char = r;code = 114
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = a;code = 97
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = L;code = 76
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = );code = 41
char = (;code = 40
char = O;code = 79
char = A;code = 65
char = c;code = 99
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = n;code = 110
char = -;code = 45
char = B;code = 66
char = u;code = 117
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = N;code = 78
char = M;code = 77
char = n;code = 110
char = O;code = 79
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = ;code = 32
char = y;code = 121
char = i;code = 105
char = e;code = 101
char = l;code = 108
char = d;code = 100
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = t;code = 116
char = e;code = 101
char = t;code = 116
char = r;code = 114
char = a;code = 97
char = m;code = 109
char = a;code = 97
char = n;code = 110
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = e;code = 101
char = s;code = 115
char = e;code = 101
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = m;code = 109
char = p;code = 112
char = o;code = 111
char = u;code = 117
char = n;code = 110
char = d;code = 100
char = ,;code = 44
char = ;code = 32
char = [;code = 91
char = M;code = 77
char = n;code = 110
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = (;code = 40
char = m;code = 109
char = u;code = 117
char = (;code = 40
char = 3;code = 51
char = );code = 41
char = -;code = 45
char = O;code = 79
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = (;code = 40
char = O;code = 79
char = A;code = 65
char = c;code = 99
char = );code = 41
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = (;code = 40
char = H;code = 72
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = O;code = 79
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = L;code = 76
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ];code = 93
char = (;code = 40
char = P;code = 80
char = F;code = 70
char = (;code = 40
char = 6;code = 54
char = );code = 41
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ;code = 32
char = x;code = 120
char = ;code = 32
char = 2;code = 50
char = ;code = 32
char = C;code = 67
char = H;code = 72
char = (;code = 40
char = 3;code = 51
char = );code = 41
char = C;code = 67
char = N;code = 78
char = ;code = 32
char = (;code = 40
char = 3;code = 51
char = );code = 41
char = .;code = 46
char = ;code = 32
char = C;code = 67
char = o;code = 111
char = m;code = 109
char = p;code = 112
char = o;code = 111
char = u;code = 117
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = 3;code = 51
char = ;code = 32
char = h;code = 104
char = a;code = 97
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = m;code = 109
char = e;code = 101
char = r;code = 114
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = m;code = 109
char = e;code = 101
char = r;code = 114
char = s;code = 115
char = ;code = 32
char = s;code = 115
char = t;code = 116
char = r;code = 114
char = u;code = 117
char = c;code = 99
char = t;code = 116
char = u;code = 117
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = e;code = 101
char = t;code = 116
char = r;code = 114
char = a;code = 97
char = n;code = 110
char = u;code = 117
char = c;code = 99
char = l;code = 108
char = e;code = 101
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = t;code = 116
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = n;code = 110
char = s;code = 115
char = i;code = 105
char = s;code = 115
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = b;code = 98
char = i;code = 105
char = n;code = 110
char = u;code = 117
char = c;code = 99
char = l;code = 108
char = e;code = 101
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = [;code = 91
char = M;code = 77
char = n;code = 110
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = O;code = 79
char = (;code = 40
char = O;code = 79
char = A;code = 65
char = c;code = 99
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = L;code = 76
char = ];code = 93
char = (;code = 40
char = +;code = 43
char = );code = 41
char = ;code = 32
char = f;code = 102
char = r;code = 114
char = a;code = 97
char = g;code = 103
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = P;code = 80
char = F;code = 70
char = (;code = 40
char = 6;code = 54
char = );code = 41
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = .;code = 46
char = ;code = 32
char = B;code = 66
char = V;code = 86
char = S;code = 83
char = ;code = 32
char = c;code = 99
char = a;code = 97
char = l;code = 108
char = c;code = 99
char = u;code = 117
char = l;code = 108
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = d;code = 100
char = i;code = 105
char = c;code = 99
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = t;code = 116
char = ;code = 32
char = 3;code = 51
char = ;code = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = m;code = 109
char = i;code = 105
char = x;code = 120
char = e;code = 101
char = d;code = 100
char = -;code = 45
char = v;code = 118
char = a;code = 97
char = l;code = 108
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = 2;code = 50
char = M;code = 77
char = n;code = 110
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = );code = 41
char = ;code = 32
char = p;code = 112
char = l;code = 108
char = u;code = 117
char = s;code = 115
char = ;code = 32
char = 2;code = 50
char = M;code = 77
char = n;code = 110
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = I;code = 73
char = );code = 41
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = m;code = 109
char = p;code = 112
char = o;code = 111
char = u;code = 117
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = w;code = 119
char = h;code = 104
char = e;code = 101
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = w;code = 119
char = o;code = 111
char = ;code = 32
char = [;code = 91
char = M;code = 77
char = n;code = 110
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = O;code = 79
char = (;code = 40
char = O;code = 79
char = A;code = 65
char = c;code = 99
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = L;code = 76
char = ];code = 93
char = (;code = 40
char = +;code = 43
char = );code = 41
char = ;code = 32
char = f;code = 102
char = r;code = 114
char = a;code = 97
char = g;code = 103
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = h;code = 104
char = e;code = 101
char = l;code = 108
char = d;code = 100
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = g;code = 103
char = e;code = 101
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = r;code = 114
char = ;code = 32
char = b;code = 98
char = y;code = 121
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = I;code = 73
char = );code = 41
char = -;code = 45
char = O;code = 79
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = -;code = 45
char = f;code = 102
char = r;code = 114
char = a;code = 97
char = g;code = 103
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = n;code = 110
char = k;code = 107
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char = r;code = 114
char = s;code = 115
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char = w;code = 119
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char = c;code = 99
char = h;code = 104
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char = h;code = 104
char = a;code = 97
char = v;code = 118
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char = a;code = 97
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = s;code = 115
char = t;code = 116
char = o;code = 111
char = r;code = 114
char = t;code = 116
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = o;code = 111
char = c;code = 99
char = t;code = 116
char = a;code = 97
char = h;code = 104
char = e;code = 101
char = d;code = 100
char = r;code = 114
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = g;code = 103
char = e;code = 101
char = o;code = 111
char = m;code = 109
char = e;code = 101
char = t;code = 116
char = r;code = 114
char = y;code = 121
char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = t;code = 116
char = o;code = 111
char = m;code = 109
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = [;code = 91
char = M;code = 77
char = n;code = 110
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = O;code = 79
char = (;code = 40
char = O;code = 79
char = A;code = 65
char = c;code = 99
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = L;code = 76
char = ];code = 93
char = (;code = 40
char = +;code = 43
char = );code = 41
char = ;code = 32
char = f;code = 102
char = r;code = 114
char = a;code = 97
char = g;code = 103
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = h;code = 104
char = a;code = 97
char = v;code = 118
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = c;code = 99
char = a;code = 97
char = p;code = 112
char = p;code = 112
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = s;code = 115
char = q;code = 113
char = u;code = 117
char = a;code = 97
char = r;code = 114
char = e;code = 101
char = -;code = 45
char = p;code = 112
char = y;code = 121
char = r;code = 114
char = a;code = 97
char = m;code = 109
char = i;code = 105
char = d;code = 100
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = n;code = 110
char = f;code = 102
char = i;code = 105
char = g;code = 103
char = u;code = 117
char = r;code = 114
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = w;code = 119
char = h;code = 104
char = e;code = 101
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = q;code = 113
char = u;code = 117
char = a;code = 97
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char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = c;code = 99
char = a;code = 97
char = p;code = 112
char = p;code = 112
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = o;code = 111
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = f;code = 102
char = a;code = 97
char = c;code = 99
char = e;code = 101
char = s;code = 115
char = .;code = 46
char = ;code = 32
char = A;code = 65
char = l;code = 108
char = t;code = 116
char = h;code = 104
char = o;code = 111
char = u;code = 117
char = g;code = 103
char = h;code = 104
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = q;code = 113
char = u;code = 117
char = a;code = 97
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = w;code = 119
char = e;code = 101
char = l;code = 108
char = l;code = 108
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = b;code = 98
char = o;code = 111
char = n;code = 110
char = d;code = 100
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = s;code = 115
char = t;code = 116
char = a;code = 97
char = n;code = 110
char = c;code = 99
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = c;code = 99
char = a;code = 97
char = r;code = 114
char = b;code = 98
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = t;code = 116
char = o;code = 111
char = m;code = 109
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = p;code = 112
char = r;code = 114
char = o;code = 111
char = x;code = 120
char = i;code = 105
char = m;code = 109
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = e;code = 101
char = t;code = 116
char = h;code = 104
char = y;code = 121
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = b;code = 98
char = r;code = 114
char = i;code = 105
char = d;code = 100
char = g;code = 103
char = e;code = 101
char = ,;code = 44
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = d;code = 100
char = o;code = 111
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = n;code = 110
char = o;code = 111
char = t;code = 116
char = ;code = 32
char = a;code = 97
char = p;code = 112
char = p;code = 112
char = e;code = 101
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = b;code = 98
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = ;code = 32
char = o;code = 111
char = x;code = 120
char = y;code = 121
char = g;code = 103
char = e;code = 101
char = n;code = 110
char = -;code = 45
char = c;code = 99
char = a;code = 97
char = r;code = 114
char = b;code = 98
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = b;code = 98
char = o;code = 111
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = f;code = 102
char = o;code = 111
char = r;code = 114
char = m;code = 109
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ,;code = 44
char = ;code = 32
char = r;code = 114
char = a;code = 97
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = r;code = 114
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
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char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
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char = d;code = 100
char = ;code = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = n;code = 110
char = s;code = 115
char = t;code = 116
char = r;code = 114
char = a;code = 97
char = i;code = 105
char = n;code = 110
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = i;code = 105
char = s;code = 115
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char = p;code = 112
char = o;code = 111
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char = i;code = 105
char = t;code = 116
char = i;code = 105
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char = ,;code = 44
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char = a;code = 97
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char = d;code = 100
char = e;code = 101
char = d;code = 100
char = u;code = 117
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char = e;code = 101
char = d;code = 100
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char = b;code = 98
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char = t;code = 116
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char = e;code = 101
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char = o;code = 111
char = b;code = 98
char = s;code = 115
char = e;code = 101
char = r;code = 114
char = v;code = 118
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char = i;code = 105
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char = a;code = 97
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char = t;code = 116
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char = l;code = 108
char = e;code = 101
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char = g;code = 103
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char = a;code = 97
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char = l;code = 108
char = e;code = 101
char = s;code = 115
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char = f;code = 102
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
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char = a;code = 97
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char = e;code = 101
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char = e;code = 101
char = s;code = 115
char = s;code = 115
char = e;code = 101
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char = i;code = 105
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = y;code = 121
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char = a;code = 97
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char = a;code = 97
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char = ;code = 32
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char = o;code = 111
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char = e;code = 101
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char = o;code = 111
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char = t;code = 116
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char = f;code = 102
char = r;code = 114
char = e;code = 101
char = e;code = 101
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char = a;code = 97
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char = d;code = 100
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char = ;code = 32
char = L;code = 76
char = .;code = 46
char = ;code = 32
char = R;code = 82
char = e;code = 101
char = a;code = 97
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
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char = o;code = 111
char = f;code = 102
char = ;code = 32
char = L;code = 76
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
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char = r;code = 114
char = a;code = 97
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char = e;code = 101
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char = t;code = 116
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char = i;code = 105
char = f;code = 102
char = l;code = 108
char = a;code = 97
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char = s;code = 115
char = a;code = 97
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char = t;code = 116
char = s;code = 115
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char = o;code = 111
char = f;code = 102
char = ;code = 32
char = F;code = 70
char = e;code = 101
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char = I;code = 73
char = I;code = 73
char = );code = 41
char = ,;code = 44
char = ;code = 32
char = M;code = 77
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char = I;code = 73
char = I;code = 73
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char = ;code = 32
char = a;code = 97
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char = d;code = 100
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char = C;code = 67
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char = I;code = 73
char = I;code = 73
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char = ;code = 32
char = i;code = 105
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char = C;code = 67
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char = S;code = 83
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char = C;code = 67
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char = C;code = 67
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char = ;code = 32
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char = 4;code = 52
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char = ,;code = 44
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char = [;code = 91
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char = 7;code = 55
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char = C;code = 67
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char = C;code = 67
char = N;code = 78
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char = 1;code = 49
char = .;code = 46
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char = E;code = 69
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char = E;code = 69
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char = C;code = 67
char = l;code = 108
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char = );code = 41
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char = 4;code = 52
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char = C;code = 67
char = H;code = 72
char = (;code = 40
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char = C;code = 67
char = N;code = 78
char = ;code = 32
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char = 2;code = 50
char = ;code = 32
char = E;code = 69
char = t;code = 116
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char = E;code = 69
char = t;code = 116
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char = 6;code = 54
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char = w;code = 119
char = h;code = 104
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char = e;code = 101
char = a;code = 97
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char = h;code = 104
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char = M;code = 77
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char = I;code = 73
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char = ;code = 32
char = c;code = 99
char = e;code = 101
char = n;code = 110
char = t;code = 116
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char = t;code = 116
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char = a;code = 97
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char = s;code = 115
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char = i;code = 105
char = g;code = 103
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char = s;code = 115
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char = t;code = 116
char = a;code = 97
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char = e;code = 101
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char = a;code = 97
char = l;code = 108
char = ;code = 32
char = g;code = 103
char = e;code = 101
char = o;code = 111
char = m;code = 109
char = e;code = 101
char = t;code = 116
char = r;code = 114
char = y;code = 121
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char = i;code = 105
char = s;code = 115
char = ;code = 32
char = b;code = 98
char = r;code = 114
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char = d;code = 100
char = g;code = 103
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = b;code = 98
char = y;code = 121
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = r;code = 114
char = e;code = 101
char = e;code = 101
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = t;code = 116
char = o;code = 111
char = p;code = 112
char = i;code = 105
char = c;code = 99
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char = l;code = 108
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char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = s;code = 115
char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = M;code = 77
char = -;code = 45
char = M;code = 77
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = s;code = 115
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char = a;code = 97
char = n;code = 110
char = c;code = 99
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = v;code = 118
char = a;code = 97
char = r;code = 114
char = i;code = 105
char = e;code = 101
char = d;code = 100
char = ;;code = 59
char = ;code = 32
char = 5;code = 53
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char = 9;code = 57
char = 6;code = 54
char = 1;code = 49
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char = A;code = 65
char = ;code = 32
char = (;code = 40
char = M;code = 77
char = n;code = 110
char = );code = 41
char = ,;code = 44
char = ;code = 32
char = 6;code = 54
char = .;code = 46
char = 2;code = 50
char = 3;code = 51
char = 3;code = 51
char = ;code = 32
char = A;code = 65
char = ;code = 32
char = (;code = 40
char = C;code = 67
char = o;code = 111
char = );code = 41
char = ;code = 32
char = 6;code = 54
char = .;code = 46
char = 3;code = 51
char = 3;code = 51
char = 1;code = 49
char = ;code = 32
char = A;code = 65
char = ;code = 32
char = (;code = 40
char = F;code = 70
char = e;code = 101
char = );code = 41
char = .;code = 46
char = ;code = 32
char = R;code = 82
char = e;code = 101
char = a;code = 97
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
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char = o;code = 111
char = f;code = 102
char = ;code = 32
char = L;code = 76
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = ;code = 32
char = C;code = 67
char = o;code = 111
char = (;code = 40
char = C;code = 67
char = l;code = 108
char = O;code = 79
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ;code = 32
char = x;code = 120
char = ;code = 32
char = 6;code = 54
char = ;code = 32
char = H;code = 72
char = (;code = 40
char = 2;code = 50
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char = O;code = 79
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = w;code = 119
char = e;code = 101
char = t;code = 116
char = ;code = 32
char = a;code = 97
char = c;code = 99
char = e;code = 101
char = t;code = 116
char = o;code = 111
char = n;code = 110
char = i;code = 105
char = t;code = 116
char = r;code = 114
char = i;code = 105
char = l;code = 108
char = e;code = 101
char = ;code = 32
char = y;code = 121
char = i;code = 105
char = e;code = 101
char = l;code = 108
char = d;code = 100
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = c;code = 99
char = o;code = 111
char = b;code = 98
char = a;code = 97
char = l;code = 108
char = t;code = 116
char = o;code = 111
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = I;code = 73
char = );code = 41
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = m;code = 109
char = p;code = 112
char = o;code = 111
char = u;code = 117
char = n;code = 110
char = d;code = 100
char = ,;code = 44
char = ;code = 32
char = [;code = 91
char = C;code = 67
char = o;code = 111
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = L;code = 76
char = ';code = 39
char = (;code = 40
char = 3;code = 51
char = );code = 41
char = (;code = 40
char = O;code = 79
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ];code = 93
char = (;code = 40
char = C;code = 67
char = l;code = 108
char = O;code = 79
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ;code = 32
char = x;code = 120
char = ;code = 32
char = H;code = 72
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = O;code = 79
char = ;code = 32
char = (;code = 40
char = 7;code = 55
char = );code = 41
char = ,;code = 44
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = ;code = 32
char = t;code = 116
char = w;code = 119
char = o;code = 111
char = ;code = 32
char = t;code = 116
char = y;code = 121
char = p;code = 112
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = L;code = 76
char = ';code = 39
char = ;code = 32
char = f;code = 102
char = r;code = 114
char = a;code = 97
char = g;code = 103
char = m;code = 109
char = e;code = 101
char = n;code = 110
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char = s;code = 115
char = ;;code = 59
char = ;code = 32
char = o;code = 111
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = b;code = 98
char = r;code = 114
char = i;code = 105
char = d;code = 100
char = g;code = 103
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = b;code = 98
char = e;code = 101
char = t;code = 116
char = w;code = 119
char = e;code = 101
char = e;code = 101
char = n;code = 110
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = w;code = 119
char = o;code = 111
char = ;code = 32
char = C;code = 67
char = o;code = 111
char = ;code = 32
char = c;code = 99
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = s;code = 115
char = ;code = 32
char = a;code = 97
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char = d;code = 100
char = ;code = 32
char = t;code = 116
char = w;code = 119
char = o;code = 111
char = ;code = 32
char = n;code = 110
char = o;code = 111
char = n;code = 110
char = -;code = 45
char = b;code = 98
char = r;code = 114
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char = d;code = 100
char = g;code = 103
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = s;code = 115
char = ,;code = 44
char = ;code = 32
char = e;code = 101
char = a;code = 97
char = c;code = 99
char = h;code = 104
char = ;code = 32
char = b;code = 98
char = o;code = 111
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = C;code = 67
char = o;code = 111
char = ;code = 32
char = a;code = 97
char = t;code = 116
char = o;code = 111
char = m;code = 109
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char = v;code = 118
char = i;code = 105
char = a;code = 97
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char = o;code = 111
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char = e;code = 101
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char = b;code = 98
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char = p;code = 112
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char = d;code = 100
char = y;code = 121
char = l;code = 108
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char = g;code = 103
char = r;code = 114
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char = u;code = 117
char = p;code = 112
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char = w;code = 119
char = h;code = 104
char = e;code = 101
char = r;code = 114
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char = ;code = 32
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char = h;code = 104
char = e;code = 101
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char = o;code = 111
char = t;code = 116
char = h;code = 104
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char = r;code = 114
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char = i;code = 105
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char = d;code = 100
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char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = o;code = 111
char = c;code = 99
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char = a;code = 97
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char = d;code = 100
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char = a;code = 97
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char = a;code = 97
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char = a;code = 97
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char = h;code = 104
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char = C;code = 67
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char = a;code = 97
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char = o;code = 111
char = m;code = 109
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char = c;code = 99
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char = o;code = 111
char = f;code = 102
char = ;code = 32
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char = c;code = 99
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char = a;code = 97
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char = b;code = 98
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char = m;code = 109
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char = o;code = 111
char = f;code = 102
char = ;code = 32
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char = e;code = 101
char = t;code = 116
char = h;code = 104
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char = m;code = 109
char = o;code = 111
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char = y;code = 121
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char = f;code = 102
char = ;code = 32
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char = b;code = 98
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char = a;code = 97
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char = a;code = 97
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char = h;code = 104
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char = L;code = 76
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char = C;code = 67
char = l;code = 108
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char = );code = 41
char = (;code = 40
char = 2;code = 50
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char = 6;code = 54
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char = f;code = 102
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char = E;code = 69
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char = 3;code = 51
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char = N;code = 78
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char = O;code = 79
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char = );code = 41
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char = C;code = 67
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result sql = A ditopic 1,2-bis(2,2'-bipyridyl-6-yl)ethyne ligand, L, has been synthesized for the first time by consecutive Suzuki and Sonogashira coupling reactions either in a one- or two-step synthesis. Coordination of L with some first-row transition metals, Fe, Mn and Co showed a very rich structural diversity that can be obtained with this ligand. Reaction of L with Mn(II)(OAc)(2) yielded a dimanganese(II) complex, [Mn(2)L(mu-OAc)(3)]PF(6), (1) where the two somewhat inequivalent trigonal-bipyramidal Mn atoms separated by 3.381 A are bridged by L and three acetate moieties. A similar reaction of L with Mn(III)(OAc)(3) yielded a very different dimanganese complex [Mn(2)L'(OH)(OAc)(2)(DMF)(2)]PF(6) x DMF (2) where L' is a E-1,2-bis(2,2'-bipyridyl-6-yl)ethene fragment that was formed in situ. The L' ligand bridges between the two Mn centers, despite its trans configuration, which leads to a very strained ethene bridging moiety. The Mn atoms are also bridged by two acetate ligands and a hydroxy group that bridges between the Mn atoms and the ethene fragment; DMF completes the octahedral coordination around each Mn atom which are separated by 3.351 A. A comproportionation reaction of L with Mn(II)(OAc)(2) and n-Bu(4)NMnO(4) yielded a tetramanganese compound, [Mn(4)(mu(3)-O)(2)(OAc)(4)(H(2)O)(2)L(2)](PF(6))(2) x 2 CH(3)CN (3). Compound 3 has a dimer of dimers structure of the tetranuclear Mn core that consists of binuclear [Mn(2)O(OAc)(2)L](+) fragment and a PF(6) anion. BVS calculations indicate that 3 is a mixed-valent 2Mn(II) plus 2Mn(III) compound where two [Mn(II)(2)O(OAc)(2)L](+) fragments are held together by Mn(III)-O inter-fragment linkers which have a distorted octahedral geometry. The Mn atoms in the [Mn(2)O(OAc)(2)L](+) fragments have a capped square-pyramid configuration where an aqua ligand is capped on one of the faces. Although the aqua ligand is well within a bonding distance to a carbon atom of the proximal ethyne bridge, there does not appear to be an oxygen-carbon bond formation, rather the ligand is constrained in this position, as deduced by the observation that the bond lengths and angles of the ligand are essentially the same as those for the free ligand, L. Reaction of L with perchlorate or triflate salts of Fe(II), Mn(II) and Co(II) in dry acetonitrile yielded binuclear triple helicate structures (2:3 metal to L ratios) [Fe(2)L(3)](CF(3)SO(3))(4) x CH(3)CN (4), [Mn(2)L(3)](ClO(4))(4) x 1.7 CH(3)CN x 1.65 EtOEt (5) and [Co(2)L(3)](ClO(4))(4) x 2 CH(3)CN x 2 EtOEt (6) where each M(II) center with a slightly distorted octahedral geometry is bridged by three of the ditopic ligands. The M-M distances varied; 5.961 A (Mn), 6.233 A (Co) 6.331 A (Fe). Reaction of L with Co(ClO(4))(2) x 6 H(2)O in wet acetonitrile yielded a dicobalto(III) compound, [Co(2)L'(3)(O)(2)](ClO(4))(2) x H(2)O (7), with two types of L' fragments; one bridging between the two Co centers and two non-bridging ligands, each bonded to a Co atom via one bipyridyl group where the other is non-bonding. The octahedral coordination sphere around each Co atom is completed by the formation of a cobalt-carbon bond from the two carbon atoms of the ethene moiety of the bridging ligand and by a hydroxy moiety that is also bonded to the ethene group of the non-bridging ligand. Reaction of L with Co(ClO(4))(2) x 6 H(2)O in dry acetonitrile in the presence of Et(3)N yielded the tetracobalto(II) complex {[Co(2)L(4)(OH)(4)](ClO(4))(4)}(2) (8) with a unique twisted square configuration of cobalt ions with Co-Co distances of 3.938 to 4.131 A. In addition to the L bridging ligand the Co atoms are linked by hydroxy moieties. Some preliminary catalytic studies showed that the Mn compounds 1 and 2 were active (high yield within 3 min) for alkene epoxidation with peracetic acid and hydrogen peroxide dismutation (catalase activity).

Publication: Dalton Trans 2010 Aug 21 ;39(31)::7266-75. :doi: 10.1039/b925129d.
Publication Date: 2010 Aug 21
Study Author(s): Madhu, Vedichi;Ekambaram, Balaraman;Shimon, Linda J W;Diskin, Yael;Leitus, Gregory;Neumann, Ronny;
Institution: Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel.
Shortcut link to this study:
A ditopic 1,2-bis(2,2'-bipyridyl-6-yl)ethyne ligand, L, has been synthesized for the first time by consecutive Suzuki and Sonogashira coupling reactions either in a one- or two-step synthesis. Coordination of L with some first-row transition metals, Fe, Mn and Co showed a very rich structural diversity that can be obtained with this ligand. Reaction of L with Mn(II)(OAc)(2) yielded a dimanganese(II) complex, [Mn(2)L(mu-OAc)(3)]PF(6), (1) where the two somewhat inequivalent trigonal-bipyramidal Mn atoms separated by 3.381 A are bridged by L and three acetate moieties. A similar reaction of L with Mn(III)(OAc)(3) yielded a very different dimanganese complex [Mn(2)L'(OH)(OAc)(2)(DMF)(2)]PF(6) x DMF (2) where L' is a E-1,2-bis(2,2'-bipyridyl-6-yl)ethene fragment that was formed in situ. The L' ligand bridges between the two Mn centers, despite its trans configuration, which leads to a very strained ethene bridging moiety. The Mn atoms are also bridged by two acetate ligands and a hydroxy group that bridges between the Mn atoms and the ethene fragment; DMF completes the octahedral coordination around each Mn atom which are separated by 3.351 A. A comproportionation reaction of L with Mn(II)(OAc)(2) and n-Bu(4)NMnO(4) yielded a tetramanganese compound, [Mn(4)(mu(3)-O)(2)(OAc)(4)(H(2)O)(2)L(2)](PF(6))(2) x 2 CH(3)CN (3). Compound 3 has a dimer of dimers structure of the tetranuclear Mn core that consists of binuclear [Mn(2)O(OAc)(2)L](+) fragment and a PF(6) anion. BVS calculations indicate that 3 is a mixed-valent 2Mn(II) plus 2Mn(III) compound where two [Mn(II)(2)O(OAc)(2)L](+) fragments are held together by Mn(III)-O inter-fragment linkers which have a distorted octahedral geometry. The Mn atoms in the [Mn(2)O(OAc)(2)L](+) fragments have a capped square-pyramid configuration where an aqua ligand is capped on one of the faces. Although the aqua ligand is well within a bonding distance to a carbon atom of the proximal ethyne bridge, there does not appear to be an oxygen-carbon bond formation, rather the ligand is constrained in this position, as deduced by the observation that the bond lengths and angles of the ligand are essentially the same as those for the free ligand, L. Reaction of L with perchlorate or triflate salts of Fe(II), Mn(II) and Co(II) in dry acetonitrile yielded binuclear triple helicate structures (2:3 metal to L ratios) [Fe(2)L(3)](CF(3)SO(3))(4) x CH(3)CN (4), [Mn(2)L(3)](ClO(4))(4) x 1.7 CH(3)CN x 1.65 EtOEt (5) and [Co(2)L(3)](ClO(4))(4) x 2 CH(3)CN x 2 EtOEt (6) where each M(II) center with a slightly distorted octahedral geometry is bridged by three of the ditopic ligands. The M-M distances varied; 5.961 A (Mn), 6.233 A (Co) 6.331 A (Fe). Reaction of L with Co(ClO(4))(2) x 6 H(2)O in wet acetonitrile yielded a dicobalto(III) compound, [Co(2)L'(3)(O)(2)](ClO(4))(2) x H(2)O (7), with two types of L' fragments; one bridging between the two Co centers and two non-bridging ligands, each bonded to a Co atom via one bipyridyl group where the other is non-bonding. The octahedral coordination sphere around each Co atom is completed by the formation of a cobalt-carbon bond from the two carbon atoms of the ethene moiety of the bridging ligand and by a hydroxy moiety that is also bonded to the ethene group of the non-bridging ligand. Reaction of L with Co(ClO(4))(2) x 6 H(2)O in dry acetonitrile in the presence of Et(3)N yielded the tetracobalto(II) complex {[Co(2)L(4)(OH)(4)](ClO(4))(4)}(2) (8) with a unique twisted square configuration of cobalt ions with Co-Co distances of 3.938 to 4.131 A. In addition to the L bridging ligand the Co atoms are linked by hydroxy moieties. Some preliminary catalytic studies showed that the Mn compounds 1 and 2 were active (high yield within 3 min) for alkene epoxidation with peracetic acid and hydrogen peroxide dismutation (catalase activity).
PMID: 20582360

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