char = A;code = 65
char = ;code = 32
char = m;code = 109
char = o;code = 111
char = l;code = 108
char = e;code = 101
char = c;code = 99
char = u;code = 117
char = l;code = 108
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = p;code = 112
char = a;code = 97
char = d;code = 100
char = d;code = 100
char = l;code = 108
char = e;code = 101
char = w;code = 119
char = h;code = 104
char = e;code = 101
char = e;code = 101
char = l;code = 108
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = s;code = 115
char = l;code = 108
char = i;code = 105
char = d;code = 100
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = o;code = 111
char = r;code = 114
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = o;code = 111
char = m;code = 109
char = e;code = 101
char = t;code = 116
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = i;code = 105
char = c;code = 99
char = ;code = 32
char = l;code = 108
char = a;code = 97
char = t;code = 116
char = c;code = 99
char = h;code = 104
char = :;code = 58
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 = s;code = 115
char = e;code = 101
char = s;code = 115
char = ,;code = 44
char = ;code = 32
char = X;code = 88
char = -;code = 45
char = r;code = 114
char = a;code = 97
char = y;code = 121
char = ;code = 32
char = c;code = 99
char = r;code = 114
char = y;code = 121
char = s;code = 115
char = t;code = 116
char = a;code = 97
char = l;code = 108
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 = s;code = 115
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = d;code = 100
char = y;code = 121
char = n;code = 110
char = a;code = 97
char = m;code = 109
char = i;code = 105
char = c;code = 99
char = ;code = 32
char = b;code = 98
char = e;code = 101
char = h;code = 104
char = a;code = 97
char = v;code = 118
char = i;code = 105
char = o;code = 111
char = u;code = 117
char = r;code = 114
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = [;code = 91
char = C;code = 67
char = r;code = 114
char = (;code = 40
char = C;code = 67
char = O;code = 79
char = );code = 41
char = 3;code = 51
char = {;code = 123
char = e;code = 101
char = t;code = 116
char = a;code = 97
char = (;code = 40
char = 6;code = 54
char = );code = 41
char = -;code = 45
char = 2;code = 50
char = -;code = 45
char = (;code = 40
char = 9;code = 57
char = -;code = 45
char = t;code = 116
char = r;code = 114
char = i;code = 105
char = p;code = 112
char = t;code = 116
char = y;code = 121
char = c;code = 99
char = y;code = 121
char = l;code = 108
char = );code = 41
char = i;code = 105
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = };code = 125
char = ];code = 93
char = ,;code = 44
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = [;code = 91
char = M;code = 77
char = (;code = 40
char = C;code = 67
char = O;code = 79
char = );code = 41
char = 3;code = 51
char = {;code = 123
char = e;code = 101
char = t;code = 116
char = a;code = 97
char = (;code = 40
char = 5;code = 53
char = );code = 41
char = -;code = 45
char = 2;code = 50
char = -;code = 45
char = (;code = 40
char = 9;code = 57
char = -;code = 45
char = t;code = 116
char = r;code = 114
char = i;code = 105
char = p;code = 112
char = t;code = 116
char = y;code = 121
char = c;code = 99
char = y;code = 121
char = l;code = 108
char = );code = 41
char = i;code = 105
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = n;code = 110
char = y;code = 121
char = l;code = 108
char = };code = 125
char = ];code = 93
char = ;code = 32
char = (;code = 40
char = M;code = 77
char = ;code = 32
char = =;code = 61
char = ;code = 32
char = M;code = 77
char = n;code = 110
char = ,;code = 44
char = ;code = 32
char = R;code = 82
char = e;code = 101
char = );code = 41
char = .;code = 46
result sql = A molecular paddlewheel with a sliding organometallic latch: syntheses, X-ray crystal structures and dynamic behaviour of [Cr(CO)3{eta(6)-2-(9-triptycyl)indene}], and of [M(CO)3{eta(5)-2-(9-triptycyl)indenyl}] (M = Mn, Re).
A molecular paddlewheel with a sliding organometallic latch: syntheses, X-ray crystal structures and dynamic behaviour of [Cr(CO)3{eta(6)-2-(9-triptycyl)indene}], and of [M(CO)3{eta(5)-2-(9-triptycyl)indenyl}] (M = Mn, Re).
char = I;code = 73
char = n;code = 110
char = ;code = 32
char = [;code = 91
char = e;code = 101
char = t;code = 116
char = a;code = 97
char = (;code = 40
char = 6;code = 54
char = );code = 41
char = -;code = 45
char = 2;code = 50
char = -;code = 45
char = (;code = 40
char = 9;code = 57
char = -;code = 45
char = t;code = 116
char = r;code = 114
char = i;code = 105
char = p;code = 112
char = t;code = 116
char = y;code = 121
char = c;code = 99
char = y;code = 121
char = l;code = 108
char = );code = 41
char = -;code = 45
char = i;code = 105
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = ];code = 93
char = t;code = 116
char = r;code = 114
char = i;code = 105
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 = y;code = 121
char = l;code = 108
char = c;code = 99
char = h;code = 104
char = r;code = 114
char = o;code = 111
char = m;code = 109
char = i;code = 105
char = u;code = 117
char = m;code = 109
char = ;code = 32
char = (;code = 40
char = 2;code = 50
char = a;code = 97
char = );code = 41
char = ,;code = 44
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = n;code = 110
char = y;code = 121
char = l;code = 108
char = -;code = 45
char = c;code = 99
char = h;code = 104
char = r;code = 114
char = o;code = 111
char = m;code = 109
char = i;code = 105
char = u;code = 117
char = m;code = 109
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 = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = n;code = 110
char = k;code = 107
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = r;code = 114
char = e;code = 101
char = c;code = 99
char = t;code = 116
char = l;code = 108
char = y;code = 121
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = x;code = 120
char = i;code = 105
char = s;code = 115
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 = h;code = 104
char = r;code = 114
char = e;code = 101
char = e;code = 101
char = -;code = 45
char = b;code = 98
char = l;code = 108
char = a;code = 97
char = d;code = 100
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = t;code = 116
char = r;code = 114
char = i;code = 105
char = p;code = 112
char = t;code = 116
char = y;code = 121
char = c;code = 99
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = p;code = 112
char = a;code = 97
char = d;code = 100
char = d;code = 100
char = l;code = 108
char = e;code = 101
char = w;code = 119
char = h;code = 104
char = e;code = 101
char = e;code = 101
char = l;code = 108
char = .;code = 46
char = ;code = 32
char = H;code = 72
char = o;code = 111
char = w;code = 119
char = e;code = 101
char = v;code = 118
char = e;code = 101
char = r;code = 114
char = ,;code = 44
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = m;code = 109
char = o;code = 111
char = l;code = 108
char = e;code = 101
char = c;code = 99
char = u;code = 117
char = l;code = 108
char = a;code = 97
char = r;code = 114
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 = 2;code = 50
char = a;code = 97
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 = s;code = 115
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = t;code = 116
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 = i;code = 105
char = s;code = 115
char = ;code = 32
char = n;code = 110
char = o;code = 111
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 = ;code = 32
char = i;code = 105
char = n;code = 110
char = t;code = 116
char = e;code = 101
char = r;code = 114
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 = 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 = 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 = n;code = 110
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = s;code = 115
char = ,;code = 44
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 = p;code = 112
char = a;code = 97
char = d;code = 100
char = d;code = 100
char = l;code = 108
char = e;code = 101
char = w;code = 119
char = h;code = 104
char = e;code = 101
char = e;code = 101
char = l;code = 108
char = ;code = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = f;code = 102
char = r;code = 114
char = e;code = 101
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = r;code = 114
char = o;code = 111
char = t;code = 116
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = .;code = 46
char = ;code = 32
char = A;code = 65
char = c;code = 99
char = c;code = 99
char = o;code = 111
char = r;code = 114
char = d;code = 100
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = l;code = 108
char = y;code = 121
char = ,;code = 44
char = ;code = 32
char = i;code = 105
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = N;code = 78
char = M;code = 77
char = R;code = 82
char = ;code = 32
char = s;code = 115
char = p;code = 112
char = e;code = 101
char = c;code = 99
char = t;code = 116
char = r;code = 114
char = u;code = 117
char = m;code = 109
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 = 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 = u;code = 117
char = l;code = 108
char = l;code = 108
char = ;code = 32
char = e;code = 101
char = q;code = 113
char = u;code = 117
char = i;code = 105
char = v;code = 118
char = a;code = 97
char = l;code = 108
char = e;code = 101
char = n;code = 110
char = c;code = 99
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 = b;code = 98
char = l;code = 108
char = a;code = 97
char = d;code = 100
char = e;code = 101
char = s;code = 115
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 = r;code = 114
char = i;code = 105
char = p;code = 112
char = t;code = 116
char = y;code = 121
char = c;code = 99
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = .;code = 46
char = ;code = 32
char = D;code = 68
char = e;code = 101
char = p;code = 112
char = r;code = 114
char = o;code = 111
char = t;code = 116
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 = 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 = i;code = 105
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = d;code = 100
char = u;code = 117
char = c;code = 99
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = h;code = 104
char = a;code = 97
char = p;code = 112
char = t;code = 116
char = o;code = 111
char = t;code = 116
char = r;code = 114
char = o;code = 111
char = p;code = 112
char = i;code = 105
char = c;code = 99
char = ;code = 32
char = s;code = 115
char = h;code = 104
char = i;code = 105
char = f;code = 102
char = t;code = 116
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 = o;code = 111
char = r;code = 114
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = o;code = 111
char = m;code = 109
char = e;code = 101
char = t;code = 116
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = i;code = 105
char = c;code = 99
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 = f;code = 102
char = r;code = 114
char = o;code = 111
char = m;code = 109
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = s;code = 115
char = i;code = 105
char = x;code = 120
char = -;code = 45
char = m;code = 109
char = e;code = 101
char = m;code = 109
char = b;code = 98
char = e;code = 101
char = r;code = 114
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = f;code = 102
char = i;code = 105
char = v;code = 118
char = e;code = 101
char = -;code = 45
char = m;code = 109
char = e;code = 101
char = m;code = 109
char = b;code = 98
char = e;code = 101
char = r;code = 114
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = r;code = 114
char = i;code = 105
char = n;code = 110
char = g;code = 103
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 = i;code = 105
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ,;code = 44
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 = s;code = 115
char = o;code = 111
char = d;code = 100
char = i;code = 105
char = u;code = 117
char = m;code = 109
char = ;code = 32
char = [;code = 91
char = e;code = 101
char = t;code = 116
char = a;code = 97
char = (;code = 40
char = 5;code = 53
char = );code = 41
char = -;code = 45
char = 2;code = 50
char = -;code = 45
char = (;code = 40
char = 9;code = 57
char = -;code = 45
char = t;code = 116
char = r;code = 114
char = i;code = 105
char = p;code = 112
char = t;code = 116
char = y;code = 121
char = c;code = 99
char = y;code = 121
char = l;code = 108
char = );code = 41
char = -;code = 45
char = i;code = 105
char = n;code = 110
char = d;code = 100
char = e;code = 101
char = n;code = 110
char = y;code = 121
char = l;code = 108
char = ];code = 93
char = t;code = 116
char = r;code = 114
char = i;code = 105
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 = y;code = 121
char = l;code = 108
char = c;code = 99
char = h;code = 104
char = r;code = 114
char = o;code = 111
char = m;code = 109
char = i;code = 105
char = u;code = 117
char = m;code = 109
char = ;code = 32
char = s;code = 115
char = a;code = 97
char = l;code = 108
char = t;code = 116
char = ;code = 32
char = (;code = 40
char = 3;code = 51
char = a;code = 97
char = );code = 41
char = ,;code = 44
char = ;code = 32
char = s;code = 115
char = o;code = 111
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 = 44
char = ;code = 32
char = r;code = 114
char = o;code = 111
char = t;code = 116
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 = t;code = 116
char = h;code = 104
char = e;code = 101
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 = 45
char = b;code = 98
char = l;code = 108
char = a;code = 97
char = d;code = 100
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = m;code = 109
char = o;code = 111
char = l;code = 108
char = e;code = 101
char = c;code = 99
char = u;code = 117
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char = e;code = 101
char = l;code = 108
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result sql = In [eta(6)-2-(9-triptycyl)-indene]tricarbonylchromium (2a), the indenyl-chromium moiety is linked directly to the axis of the three-bladed triptycene paddlewheel. However, the molecular structure of 2a reveals that there is no steric interaction between these components, and the paddlewheel is free to rotate. Accordingly, its NMR spectrum indicates the full equivalence of the blades of the triptycene. Deprotonation of the indene induces a haptotropic shift of the organometallic fragment from the six-membered to the five-membered ring of the indene and, in the sodium [eta(5)-2-(9-triptycyl)-indenyl]tricarbonylchromium salt (3a), so formed, rotation of the three-bladed molecular paddlewheel is now blocked by the bulky tripod. NMR data for 3a, and also for the isostructural eta(5)-Mn(CO)(3) and eta(5)-Re(CO)(3) complexes, 3b and 3c, respectively, reveal a 2:1 splitting of the blades of the triptycyl moiety, thus breaking its original threefold symmetry. The X-ray crystal structures of the chromium complex, 2a, and of the manganese and rhenium complexes, 3b and 3c, provide pictures of the system in both its "ON" and "OFF" states, whereby the M(CO)(3) tripod has moved about 2 A towards the triptycene, thus blocking its rotation. Comparison of the rotational barriers in 2-(9-triptycyl)indene (1) and its complexes 2 and 3, suggests that rotation of the paddlewheel can be slowed by a factor of approximately 10(8).

Publication: Chemistry 2009 ;15(8)::1836-43. :doi: 10.1002/chem.200801940.
Publication Date: 2009
Study Author(s): Nikitin, Kirill;Müller-Bunz, Helge;Ortin, Yannick;McGlinchey, Michael J;
Institution: School of Chemistry & Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland. [email protected]
Shortcut link to this study:
In [eta(6)-2-(9-triptycyl)-indene]tricarbonylchromium (2a), the indenyl-chromium moiety is linked directly to the axis of the three-bladed triptycene paddlewheel. However, the molecular structure of 2a reveals that there is no steric interaction between these components, and the paddlewheel is free to rotate. Accordingly, its NMR spectrum indicates the full equivalence of the blades of the triptycene. Deprotonation of the indene induces a haptotropic shift of the organometallic fragment from the six-membered to the five-membered ring of the indene and, in the sodium [eta(5)-2-(9-triptycyl)-indenyl]tricarbonylchromium salt (3a), so formed, rotation of the three-bladed molecular paddlewheel is now blocked by the bulky tripod. NMR data for 3a, and also for the isostructural eta(5)-Mn(CO)(3) and eta(5)-Re(CO)(3) complexes, 3b and 3c, respectively, reveal a 2:1 splitting of the blades of the triptycyl moiety, thus breaking its original threefold symmetry. The X-ray crystal structures of the chromium complex, 2a, and of the manganese and rhenium complexes, 3b and 3c, provide pictures of the system in both its "ON" and "OFF" states, whereby the M(CO)(3) tripod has moved about 2 A towards the triptycene, thus blocking its rotation. Comparison of the rotational barriers in 2-(9-triptycyl)indene (1) and its complexes 2 and 3, suggests that rotation of the paddlewheel can be slowed by a factor of approximately 10(8).
PMID: 19152350

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