Structural characterization of[Ru3(CO)10{μ1-gh2-cis-1,2-bis (diphenylphosphino)ethene}]
Resource
Journal of Organometallic Chemistry 453 (1): 133-138
Journal
Journal of Organometallic Chemistry
Journal Volume
453
Journal Issue
1
Pages
133-138
Date Issued
1993
Author(s)
Abstract
The structure of [Ru3(CO)10(μ1-η2-c-dpp) = cis-1,2-bis(diphenylphosphino)ethene) has been determined by X-ray crystallography. The crystals are monoclinic, space group P21/n, with cell dimensions: a = 10.4590(17), b = 24.197(6), c = 14.500(4) Å, β = 100.003 (22)° and Z = 4. This structure was refined to give R = 0.031 and Rw = 0.028 using 5052 reflections with I > 2σ-(I) in the range of 2 ≤ 2θ ≤ 50° (Mo Kα). The structure suggested previously to contain a 1,2-bridging c-dpp ligand is now found to contain the ligand in a 1,1-chelating geometry, which is also maintained in solution as indicated by the large downfield 31P coordination shift. This five-membered chelate ring is not perpendicular as observed for a similar ring in [Ru3(CO)10(μ1-η2-bipy)] (bipy = 2,2′-bipyridine) but nearly coplanar with the Ru3 plane. The synthesis and the structures of [M3(CO)10,(LL)] and [M2(CO)6(LL)] (M Fe, Ru or Os; LL = chelating c-dpp or bridging 1,2-bis(dimethylarsino)tetrafluorocyclobutene) are compared and a general reaction mechanism from [M3(CO)12] to [M3(CO)10(LL)] and [M2(CO)6(LL)] is proposed. © 1993.
Type
journal article