TY - JOUR
T1 - Asymmetrically Bonded η Ligands. I. Hinging away from Metal of Substituted Allyls: Synthesis of 1-syn-Methyl and -Phenyl Complexes and the Molecular Structures of [(η-1-Ph-C3H4)Pd(tmeda)]BF4, [(η-C5H5)Pd(η-1-Ph-C3H4)] and [(phen)Mo(CO)2(NCS)(η-1-Ph-C3H4)] at 185K
AU - Murrall, Nicholas W.
AU - Welch, Alan J.
PY - 1986/1/18
Y1 - 1986/1/18
N2 - Seven new complexes of (η-1-Me-C3H4) and (η-1-Ph-C3H4) with symmetric metal ligand backbones have been synthesised and spectroscopically characterised. Crystals of three of them, [(η-1-Ph-C3H4)Pd(tmeda)]BF4 (4), [(η-C5H5Pd(η-1-Ph-C3H4)] (5), and [(phen)Mo(CO)2(NCS)(η-1-Ph-C3H4)] (8), were suitable for X-ray diffraction studies. 4 is orthorhombic, Pca1, with four ion pairs in a cell of dimensions a 11.326(4), b 16.048(5), and c 9.950(3) Å. Using 4431 data measured at 185 K, R converged at 0.0311. Crystals of 5 are monoclinic, P21/c, with a 14.2255(19), b 5.8203(11), c 13.837(5) Å, and β 91.287(21°) at 185 K, Z = 4. 3064 amplitudes have been used to afford R = 0.0267. For 8 the monoclinic cell is a 15.658(4), b 9.473(3), c 15.666(6) Å, and β 113.95(3)°, P21/a, Z = 4. Low temperature (185 K) data were collected, and 3734 used to refine the structure to R = 0.0362. The molecular structures of 4, 5, and 8 all reveal an η-1-syn-Ph-C3H4 ligand that is asymmetrically bonded to the metal atom, such that M-C(l) > M-C(3). Analysis of intra- and intermolecular contacts strongly suggests that, at least for 5, the distortion in the metal-allyl bonding is electronic in origin.
AB - Seven new complexes of (η-1-Me-C3H4) and (η-1-Ph-C3H4) with symmetric metal ligand backbones have been synthesised and spectroscopically characterised. Crystals of three of them, [(η-1-Ph-C3H4)Pd(tmeda)]BF4 (4), [(η-C5H5Pd(η-1-Ph-C3H4)] (5), and [(phen)Mo(CO)2(NCS)(η-1-Ph-C3H4)] (8), were suitable for X-ray diffraction studies. 4 is orthorhombic, Pca1, with four ion pairs in a cell of dimensions a 11.326(4), b 16.048(5), and c 9.950(3) Å. Using 4431 data measured at 185 K, R converged at 0.0311. Crystals of 5 are monoclinic, P21/c, with a 14.2255(19), b 5.8203(11), c 13.837(5) Å, and β 91.287(21°) at 185 K, Z = 4. 3064 amplitudes have been used to afford R = 0.0267. For 8 the monoclinic cell is a 15.658(4), b 9.473(3), c 15.666(6) Å, and β 113.95(3)°, P21/a, Z = 4. Low temperature (185 K) data were collected, and 3734 used to refine the structure to R = 0.0362. The molecular structures of 4, 5, and 8 all reveal an η-1-syn-Ph-C3H4 ligand that is asymmetrically bonded to the metal atom, such that M-C(l) > M-C(3). Analysis of intra- and intermolecular contacts strongly suggests that, at least for 5, the distortion in the metal-allyl bonding is electronic in origin.
UR - http://www.scopus.com/inward/record.url?scp=0000167974&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(86)82060-5
DO - 10.1016/0022-328X(86)82060-5
M3 - Article
AN - SCOPUS:0000167974
SN - 0022-328X
VL - 301
SP - 109
EP - 130
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -