Solid state structure and reactivity in solution. 8. Implications of the structure of [1,2-bis(diphenylphosphino)ethane] tetra-carbonylmolybdenum(0) to the chelate effect

Add time:08/21/2019    Source:sciencedirect.com

The structure of (diphos)Mo(CO)4 (diphos=1,2- bis(diphenylphosphino)ethane) has been determined by single crystal X-ray crystallography. The crystals are orthorhombic with a=22.600(8), b=16.799(4) and c=14.587(4) Å, space group Pbca, Dcalc.=1.45 g cm−3 and Z=8. The structure was solved by the Patterson technique and refined by full-matrix least- squares methods to R=0.044 using 2206 reflections measured on a four-circle diffractometer. The coordination about the central molybdenum atom is a distorted octahedron, the greatest deviation from ideal geometry being the P1-Mo-P2 angle (80.2(1)°). Other distortions are induced through steric interaction between the phenyl and the carbonyl groups. The structure of (diphos)Mo(CO)4 is compared to that previously reported for cis- (MePh2P)2Mo(CO)4; the two molecules differ only that two methyl groups of the latter complex are replaced by the CH2CH2 backbone in the former. The influence of this difference is discussed both in terms of molecular distortions induced by the presence of the chelate ring and their influence on reactivity via chelate ring-opening and -closure.

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