|
|
char = M;code = 77
char = o;code = 111
char = d;code = 100
char = e;code = 101
char = l;code = 108
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = d;code = 100
char = i;code = 105
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 = a;code = 97
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = v;code = 118
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = n;code = 110
char = g;code = 103
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 = i;code = 105
char = n;code = 110
char = ;code = 32
char = n;code = 110
char = o;code = 111
char = n;code = 110
char = -;code = 45
char = h;code = 104
char = e;code = 101
char = m;code = 109
char = e;code = 101
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = e;code = 101
char = n;code = 110
char = z;code = 122
char = y;code = 121
char = m;code = 109
char = e;code = 101
char = s;code = 115
char = :;code = 58
char = ;code = 32
char = c;code = 99
char = a;code = 97
char = r;code = 114
char = b;code = 98
char = o;code = 111
char = x;code = 120
char = y;code = 121
char = l;code = 108
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = ;code = 32
char = s;code = 115
char = h;code = 104
char = i;code = 105
char = f;code = 102
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = (;code = 40
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 = l;code = 108
char = e;code = 101
char = x;code = 120
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = s;code = 115
char = u;code = 117
char = p;code = 112
char = p;code = 112
char = o;code = 111
char = r;code = 114
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 = s;code = 115
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = i;code = 105
char = c;code = 99
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = y;code = 121
char = ;code = 32
char = h;code = 104
char = i;code = 105
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = r;code = 114
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = c;code = 99
char = a;code = 97
char = r;code = 114
char = b;code = 98
char = o;code = 111
char = x;code = 120
char = y;code = 121
char = l;code = 108
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 = 46
result sql = Modeling dioxygen-activating centers in non-heme diiron enzymes: carboxylate shifts in diiron(II) complexes supported by sterically hindered carboxylate ligands.
Modeling dioxygen-activating centers in non-heme diiron enzymes: carboxylate shifts in diiron(II) complexes supported by sterically hindered carboxylate ligands.char = G;code = 71
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = r;code = 114
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = s;code = 115
char = y;code = 121
char = n;code = 110
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = t;code = 116
char = i;code = 105
char = c;code = 99
char = ;code = 32
char = r;code = 114
char = o;code = 111
char = u;code = 117
char = t;code = 116
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = d;code = 100
char = e;code = 101
char = s;code = 115
char = c;code = 99
char = r;code = 114
char = i;code = 105
char = b;code = 98
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = f;code = 102
char = o;code = 111
char = r;code = 114
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = s;code = 115
char = e;code = 101
char = r;code = 114
char = i;code = 105
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = (;code = 40
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 = l;code = 108
char = e;code = 101
char = x;code = 120
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = s;code = 115
char = u;code = 117
char = p;code = 112
char = p;code = 112
char = o;code = 111
char = r;code = 114
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 = s;code = 115
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = i;code = 105
char = c;code = 99
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = y;code = 121
char = ;code = 32
char = d;code = 100
char = e;code = 101
char = m;code = 109
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = c;code = 99
char = a;code = 97
char = r;code = 114
char = b;code = 98
char = o;code = 111
char = x;code = 120
char = y;code = 121
char = l;code = 108
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 = 2;code = 50
char = ,;code = 44
char = 6;code = 54
char = -;code = 45
char = d;code = 100
char = i;code = 105
char = (;code = 40
char = p;code = 112
char = -;code = 45
char = t;code = 116
char = o;code = 111
char = l;code = 108
char = y;code = 121
char = l;code = 108
char = );code = 41
char = b;code = 98
char = e;code = 101
char = n;code = 110
char = z;code = 122
char = o;code = 111
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = ;code = 32
char = (;code = 40
char = A;code = 65
char = r;code = 114
char = (;code = 40
char = T;code = 84
char = o;code = 111
char = l;code = 108
char = );code = 41
char = C;code = 67
char = O;code = 79
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = (;code = 40
char = -;code = 45
char = );code = 41
char = );code = 41
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = 2;code = 50
char = ,;code = 44
char = 6;code = 54
char = -;code = 45
char = d;code = 100
char = i;code = 105
char = (;code = 40
char = 4;code = 52
char = -;code = 45
char = f;code = 102
char = l;code = 108
char = u;code = 117
char = o;code = 111
char = r;code = 114
char = o;code = 111
char = p;code = 112
char = h;code = 104
char = e;code = 101
char = n;code = 110
char = y;code = 121
char = l;code = 108
char = );code = 41
char = b;code = 98
char = e;code = 101
char = n;code = 110
char = z;code = 122
char = o;code = 111
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = ;code = 32
char = (;code = 40
char = A;code = 65
char = r;code = 114
char = (;code = 40
char = 4;code = 52
char = -;code = 45
char = F;code = 70
char = P;code = 80
char = h;code = 104
char = );code = 41
char = C;code = 67
char = O;code = 79
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = (;code = 40
char = -;code = 45
char = );code = 41
char = );code = 41
char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = l;code = 108
char = o;code = 111
char = c;code = 99
char = k;code = 107
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = n;code = 110
char = a;code = 97
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 = m;code = 109
char = -;code = 45
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = p;code = 112
char = h;code = 104
char = e;code = 101
char = n;code = 110
char = y;code = 121
char = l;code = 108
char = ;code = 32
char = u;code = 117
char = n;code = 110
char = i;code = 105
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = s;code = 115
char = e;code = 101
char = l;code = 108
char = f;code = 102
char = -;code = 45
char = a;code = 97
char = s;code = 115
char = s;code = 115
char = e;code = 101
char = m;code = 109
char = b;code = 98
char = l;code = 108
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = [;code = 91
char = F;code = 70
char = e;code = 101
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = (;code = 40
char = m;code = 109
char = u;code = 117
char = -;code = 45
char = O;code = 79
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = C;code = 67
char = A;code = 65
char = r;code = 114
char = (;code = 40
char = T;code = 84
char = o;code = 111
char = l;code = 108
char = );code = 41
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = (;code = 40
char = O;code = 79
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = C;code = 67
char = A;code = 65
char = r;code = 114
char = (;code = 40
char = T;code = 84
char = o;code = 111
char = l;code = 108
char = );code = 41
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 = 32
char = (;code = 40
char = L;code = 76
char = ;code = 32
char = =;code = 61
char = ;code = 32
char = C;code = 67
char = (;code = 40
char = 5;code = 53
char = );code = 41
char = H;code = 72
char = (;code = 40
char = 5;code = 53
char = );code = 41
char = N;code = 78
char = ;code = 32
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = ;;code = 59
char = ;code = 32
char = 1;code = 49
char = -;code = 45
char = M;code = 77
char = e;code = 101
char = I;code = 73
char = m;code = 109
char = ;code = 32
char = (;code = 40
char = 5;code = 53
char = );code = 41
char = );code = 41
char = ;code = 32
char = p;code = 112
char = r;code = 114
char = o;code = 111
char = m;code = 109
char = o;code = 111
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 = 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 = 32
char = o;code = 111
char = f;code = 102
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 = 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 = i;code = 105
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = a;code = 97
char = l;code = 108
char = o;code = 111
char = g;code = 103
char = o;code = 111
char = u;code = 117
char = s;code = 115
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = o;code = 111
char = s;code = 115
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 = n;code = 110
char = o;code = 111
char = n;code = 110
char = -;code = 45
char = h;code = 104
char = e;code = 101
char = m;code = 109
char = e;code = 101
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = r;code = 114
char = e;code = 101
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 = e;code = 101
char = n;code = 110
char = z;code = 122
char = y;code = 121
char = m;code = 109
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = R;code = 82
char = N;code = 78
char = R;code = 82
char = -;code = 45
char = R;code = 82
char = 2;code = 50
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = D;code = 68
char = e;code = 101
char = l;code = 108
char = t;code = 116
char = a;code = 97
char = ;code = 32
char = 9;code = 57
char = D;code = 68
char = .;code = 46
char = ;code = 32
char = M;code = 77
char = a;code = 97
char = g;code = 103
char = n;code = 110
char = e;code = 101
char = t;code = 116
char = i;code = 105
char = c;code = 99
char = ;code = 32
char = s;code = 115
char = u;code = 117
char = s;code = 115
char = c;code = 99
char = e;code = 101
char = p;code = 112
char = t;code = 116
char = i;code = 105
char = b;code = 98
char = i;code = 105
char = l;code = 108
char = i;code = 105
char = t;code = 116
char = y;code = 121
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = M;code = 77
char = &;code = 38
char = #;code = 35
char = 2;code = 50
char = 4;code = 52
char = 6;code = 54
char = ;;code = 59
char = s;code = 115
char = s;code = 115
char = b;code = 98
char = a;code = 97
char = u;code = 117
char = e;code = 101
char = r;code = 114
char = ;code = 32
char = s;code = 115
char = t;code = 116
char = u;code = 117
char = d;code = 100
char = i;code = 105
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = 4;code = 52
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = 5;code = 53
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = v;code = 118
char = e;code = 101
char = a;code = 97
char = l;code = 108
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = p;code = 112
char = r;code = 114
char = o;code = 111
char = p;code = 112
char = e;code = 101
char = r;code = 114
char = t;code = 116
char = i;code = 105
char = e;code = 101
char = s;code = 115
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 = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = ;code = 32
char = w;code = 119
char = e;code = 101
char = a;code = 97
char = k;code = 107
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = t;code = 116
char = i;code = 105
char = f;code = 102
char = e;code = 101
char = r;code = 114
char = r;code = 114
char = o;code = 111
char = m;code = 109
char = a;code = 97
char = g;code = 103
char = n;code = 110
char = e;code = 101
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char = i;code = 105
char = c;code = 99
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = u;code = 117
char = p;code = 112
char = l;code = 108
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 = h;code = 104
char = i;code = 105
char = g;code = 103
char = h;code = 104
char = -;code = 45
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char = p;code = 112
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = );code = 41
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 = 46
char = ;code = 32
char = S;code = 83
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 = a;code = 97
char = l;code = 108
char = ;code = 32
char = s;code = 115
char = t;code = 116
char = u;code = 117
char = d;code = 100
char = i;code = 105
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = s;code = 115
char = e;code = 101
char = v;code = 118
char = e;code = 101
char = r;code = 114
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = d;code = 100
char = e;code = 101
char = r;code = 114
char = i;code = 105
char = v;code = 118
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = v;code = 118
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = b;code = 98
char = t;code = 116
char = a;code = 97
char = i;code = 105
char = n;code = 110
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = b;code = 98
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char = l;code = 108
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char = g;code = 103
char = a;code = 97
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char = d;code = 100
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char = b;code = 98
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char = i;code = 105
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char = u;code = 117
char = t;code = 116
char = i;code = 105
char = o;code = 111
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result sql = General synthetic routes are described for a series of diiron(II) complexes supported by sterically demanding carboxylate ligands 2,6-di(p-tolyl)benzoate (Ar(Tol)CO(2)(-)) and 2,6-di(4-fluorophenyl)benzoate (Ar(4-FPh)CO(2)(-)). The interlocking nature of the m-terphenyl units in self-assembled [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)L(2)] (L = C(5)H(5)N (4); 1-MeIm (5)) promotes the formation of coordination geometries analogous to those of the non-heme diiron cores in the enzymes RNR-R2 and Delta 9D. Magnetic susceptibility and Mössbauer studies of 4 and 5 revealed properties consistent with weak antiferromagnetic coupling between the high-spin iron(II) centers. Structural studies of several derivatives obtained by ligand substitution reactions demonstrated that the [Fe(2)(O(2)CAr')(4)L(2)] (Ar' = Ar(Tol); Ar(4-FPh)) module is geometrically flexible. Details of ligand migration within the tetracarboxylate diiron core, facilitated by carboxylate shifts, were probed by solution variable-temperature (19)F NMR spectroscopic studies of [Fe(2)(mu-O(2)CAr(4-FPh))(2)-(O(2)CAr(4-FPh))(2)(THF)(2)] (8) and [Fe(2)(mu-O(2)CAr(4-FPh))(4)(4-(t)BuC(5)H(4)N)(2)] (12). Dynamic motion in the primary coordination sphere controls the positioning of open sites and regulates the access of exogenous ligands, processes that also occur in non-heme diiron enzymes during catalysis.
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result sql = Modeling dioxygen-activating centers in non-heme diiron enzymes: carboxylate shifts in diiron(II) complexes supported by sterically hindered carboxylate ligands.
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char = a;code = 97
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char = l;code = 108
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char = d;code = 100
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char = i;code = 105
char = n;code = 110
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char = ;code = 32
char = c;code = 99
char = a;code = 97
char = r;code = 114
char = b;code = 98
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char = x;code = 120
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char = l;code = 108
char = a;code = 97
char = t;code = 116
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char = l;code = 108
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char = a;code = 97
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char = s;code = 115
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char = 2;code = 50
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char = d;code = 100
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char = p;code = 112
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char = t;code = 116
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char = l;code = 108
char = );code = 41
char = b;code = 98
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char = n;code = 110
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char = a;code = 97
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char = e;code = 101
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char = (;code = 40
char = A;code = 65
char = r;code = 114
char = (;code = 40
char = T;code = 84
char = o;code = 111
char = l;code = 108
char = );code = 41
char = C;code = 67
char = O;code = 79
char = (;code = 40
char = 2;code = 50
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char = (;code = 40
char = -;code = 45
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char = );code = 41
char = ;code = 32
char = a;code = 97
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char = ;code = 32
char = 2;code = 50
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char = d;code = 100
char = i;code = 105
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char = 4;code = 52
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char = l;code = 108
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char = o;code = 111
char = p;code = 112
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char = y;code = 121
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char = a;code = 97
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char = A;code = 65
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char = 4;code = 52
char = -;code = 45
char = F;code = 70
char = P;code = 80
char = h;code = 104
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char = C;code = 67
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char = 2;code = 50
char = );code = 41
char = (;code = 40
char = -;code = 45
char = );code = 41
char = );code = 41
char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = l;code = 108
char = o;code = 111
char = c;code = 99
char = k;code = 107
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char = n;code = 110
char = g;code = 103
char = ;code = 32
char = n;code = 110
char = a;code = 97
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 = m;code = 109
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char = e;code = 101
char = r;code = 114
char = p;code = 112
char = h;code = 104
char = e;code = 101
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char = y;code = 121
char = l;code = 108
char = ;code = 32
char = u;code = 117
char = n;code = 110
char = i;code = 105
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = n;code = 110
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char = s;code = 115
char = e;code = 101
char = l;code = 108
char = f;code = 102
char = -;code = 45
char = a;code = 97
char = s;code = 115
char = s;code = 115
char = e;code = 101
char = m;code = 109
char = b;code = 98
char = l;code = 108
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = [;code = 91
char = F;code = 70
char = e;code = 101
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = (;code = 40
char = m;code = 109
char = u;code = 117
char = -;code = 45
char = O;code = 79
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char = 2;code = 50
char = );code = 41
char = C;code = 67
char = A;code = 65
char = r;code = 114
char = (;code = 40
char = T;code = 84
char = o;code = 111
char = l;code = 108
char = );code = 41
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = (;code = 40
char = O;code = 79
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = C;code = 67
char = A;code = 65
char = r;code = 114
char = (;code = 40
char = T;code = 84
char = o;code = 111
char = l;code = 108
char = );code = 41
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 = 32
char = (;code = 40
char = L;code = 76
char = ;code = 32
char = =;code = 61
char = ;code = 32
char = C;code = 67
char = (;code = 40
char = 5;code = 53
char = );code = 41
char = H;code = 72
char = (;code = 40
char = 5;code = 53
char = );code = 41
char = N;code = 78
char = ;code = 32
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = ;;code = 59
char = ;code = 32
char = 1;code = 49
char = -;code = 45
char = M;code = 77
char = e;code = 101
char = I;code = 73
char = m;code = 109
char = ;code = 32
char = (;code = 40
char = 5;code = 53
char = );code = 41
char = );code = 41
char = ;code = 32
char = p;code = 112
char = r;code = 114
char = o;code = 111
char = m;code = 109
char = o;code = 111
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char = e;code = 101
char = s;code = 115
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
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char = f;code = 102
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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
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char = o;code = 111
char = f;code = 102
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
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char = a;code = 97
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char = i;code = 105
char = o;code = 111
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char = g;code = 103
char = e;code = 101
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char = m;code = 109
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char = t;code = 116
char = r;code = 114
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char = e;code = 101
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = a;code = 97
char = l;code = 108
char = o;code = 111
char = g;code = 103
char = o;code = 111
char = u;code = 117
char = s;code = 115
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char = t;code = 116
char = o;code = 111
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = o;code = 111
char = s;code = 115
char = e;code = 101
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char = o;code = 111
char = f;code = 102
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
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char = n;code = 110
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char = n;code = 110
char = -;code = 45
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char = e;code = 101
char = m;code = 109
char = e;code = 101
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char = r;code = 114
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char = n;code = 110
char = ;code = 32
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char = o;code = 111
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char = e;code = 101
char = s;code = 115
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char = i;code = 105
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char = t;code = 116
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char = e;code = 101
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char = z;code = 122
char = y;code = 121
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char = e;code = 101
char = s;code = 115
char = ;code = 32
char = R;code = 82
char = N;code = 78
char = R;code = 82
char = -;code = 45
char = R;code = 82
char = 2;code = 50
char = ;code = 32
char = a;code = 97
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char = D;code = 68
char = e;code = 101
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char = a;code = 97
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char = 9;code = 57
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char = a;code = 97
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char = i;code = 105
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char = s;code = 115
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char = M;code = 77
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char = #;code = 35
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char = 4;code = 52
char = 6;code = 54
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char = b;code = 98
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char = ;code = 32
char = a;code = 97
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char = e;code = 101
char = a;code = 97
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char = e;code = 101
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char = c;code = 99
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char = s;code = 115
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char = a;code = 97
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char = h;code = 104
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char = o;code = 111
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char = I;code = 73
char = I;code = 73
char = );code = 41
char = ;code = 32
char = c;code = 99
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char = e;code = 101
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char = s;code = 115
char = .;code = 46
char = ;code = 32
char = S;code = 83
char = t;code = 116
char = r;code = 114
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char = c;code = 99
char = t;code = 116
char = u;code = 117
char = r;code = 114
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 = (;code = 40
char = O;code = 79
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char = C;code = 67
char = A;code = 65
char = r;code = 114
char = ';code = 39
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char = 4;code = 52
char = );code = 41
char = L;code = 76
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char = A;code = 65
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char = =;code = 61
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char = a;code = 97
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result sql = General synthetic routes are described for a series of diiron(II) complexes supported by sterically demanding carboxylate ligands 2,6-di(p-tolyl)benzoate (Ar(Tol)CO(2)(-)) and 2,6-di(4-fluorophenyl)benzoate (Ar(4-FPh)CO(2)(-)). The interlocking nature of the m-terphenyl units in self-assembled [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)L(2)] (L = C(5)H(5)N (4); 1-MeIm (5)) promotes the formation of coordination geometries analogous to those of the non-heme diiron cores in the enzymes RNR-R2 and Delta 9D. Magnetic susceptibility and Mössbauer studies of 4 and 5 revealed properties consistent with weak antiferromagnetic coupling between the high-spin iron(II) centers. Structural studies of several derivatives obtained by ligand substitution reactions demonstrated that the [Fe(2)(O(2)CAr')(4)L(2)] (Ar' = Ar(Tol); Ar(4-FPh)) module is geometrically flexible. Details of ligand migration within the tetracarboxylate diiron core, facilitated by carboxylate shifts, were probed by solution variable-temperature (19)F NMR spectroscopic studies of [Fe(2)(mu-O(2)CAr(4-FPh))(2)-(O(2)CAr(4-FPh))(2)(THF)(2)] (8) and [Fe(2)(mu-O(2)CAr(4-FPh))(4)(4-(t)BuC(5)H(4)N)(2)] (12). Dynamic motion in the primary coordination sphere controls the positioning of open sites and regulates the access of exogenous ligands, processes that also occur in non-heme diiron enzymes during catalysis.
Publication: Inorg Chem 2002 May 20 ;41(10)::2704-19.
Publication Date: 2002 May 20
Study Author(s): Lee, Dongwhan;Lippard, Stephen J;
Institution: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Shortcut link to this study:
Publication Date: 2002 May 20
Study Author(s): Lee, Dongwhan;Lippard, Stephen J;
Institution: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Shortcut link to this study:
General synthetic routes are described for a series of diiron(II) complexes supported by sterically demanding carboxylate ligands 2,6-di(p-tolyl)benzoate (Ar(Tol)CO(2)(-)) and 2,6-di(4-fluorophenyl)benzoate (Ar(4-FPh)CO(2)(-)). The interlocking nature of the m-terphenyl units in self-assembled [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)L(2)] (L = C(5)H(5)N (4); 1-MeIm (5)) promotes the formation of coordination geometries analogous to those of the non-heme diiron cores in the enzymes RNR-R2 and Delta 9D. Magnetic susceptibility and Mössbauer studies of 4 and 5 revealed properties consistent with weak antiferromagnetic coupling between the high-spin iron(II) centers. Structural studies of several derivatives obtained by ligand substitution reactions demonstrated that the [Fe(2)(O(2)CAr')(4)L(2)] (Ar' = Ar(Tol); Ar(4-FPh)) module is geometrically flexible. Details of ligand migration within the tetracarboxylate diiron core, facilitated by carboxylate shifts, were probed by solution variable-temperature (19)F NMR spectroscopic studies of [Fe(2)(mu-O(2)CAr(4-FPh))(2)-(O(2)CAr(4-FPh))(2)(THF)(2)] (8) and [Fe(2)(mu-O(2)CAr(4-FPh))(4)(4-(t)BuC(5)H(4)N)(2)] (12). Dynamic motion in the primary coordination sphere controls the positioning of open sites and regulates the access of exogenous ligands, processes that also occur in non-heme diiron enzymes during catalysis.
PMID: 12005495
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