150576-67-3Relevant academic research and scientific papers
A-frame vs. open-book geometries in binuclear complexes bridged by diphosphines and mercaptothiazolinate ligands. Unusual examples involving a bridging bis(diphenylphosphino)ethane group
Xiao, Jianliang,Cowie, Martin
, p. 726 - 737 (2007/10/02)
Reaction of the tetracarbonyl species 2 (M = Rh, Ir; mtz = 2-mercaptothiazolinate) with 1 equivalent of the diphosphines (Ph2P(CH2)nPPh2; n = 1 (dppm), 2 (dppe)) yields the compounds (M = Rh, L = dppm (1), dppe (3); M = Ir, L = dppm (2)), which readily undergo oxidative addition of iodine to give (M = Rh, L = dppm (4), dppe (6); M = Ir, L = dppm (5)).When 2 equivalents of dppm are used, the A-frame compounds 1-mtz)(μ-mtz)(dppm)2> (M = Rh (7), Ir (8)) are afforded.In solution the dangling mtz group of 7 undergoes exchange with both the free mtz anion and the bridging mtz ligand.Compounds 7 and 8 are also produced by treatment of trans-2 (M = Rh, Ir) with 2 equivalents of the mtz anion.Reaction of these dppm-bridged dichloro species with 1 equivalent of the mtz anion yields (M = Rh (9a), Ir (10)).Compound 9a undergoes reversible Cl(1-) dissociation to give (9b), which is also the stable form in the solid.Reactin of 9 with CO gives the carbonyl-bridged species .The structures of 6 and 9b have been determined by X-ray crystallography.Compound 6 crystallizes in the triclinic space group P1(*) with one-half equivalent of THF per asymmetric unit in a cell having a = 9.856(3) Angstroem, b = 14.078(6) Angstroem, c = 16.245(5) Angstroem, α = 103.66(3) deg, β = 93.21(3) deg, γ = 92.91(3) deg, V = 2182(1) Angstroem3, and Z = 2, and has refined to R = 0.045 and Rw = 0.057 on the basis of 433 parameters varied.Compound 9b crystallizes with one equivalent of CH2Cl2 in the monoclinic space group P21/n with a = 11.400(1) Angstroem, b = 21.944(2) Angstroem, c = 22.134(1) Angstroem, β = 92.494(7) deg, V = 5532(1) Angstroem3, and Z = 4, and has refined to R = 0.062 and Rw = 0.082 on the basis of 613 parameters varied.
