149236-58-8Relevant academic research and scientific papers
Heterodinuclear bis(diphenylphosphino)methane-bridged molybdenum(d6)-palladium(d8) complexes with dative Mo→Pd bonding
Balch, Alan L.,Noll, Bruce C.,Olmstead, Marilyn M.,Toronto, Dawn V.
, p. 3613 - 3619 (2008/10/08)
Investigation of the reaction between (t-BuNC)2PdCl2 and mer-Mo(dpm-P,P′)(dpm-P)(CO)3 (dpm = bis-(diphenylphosphino)methane) has produced two complexes that combine a d6 and a d8 metal center. The reaction in dichloromethane yields green [(t-BuNC)(OC)3Mo(μ-dpm)2PdCl]Cl (6). Addition of 1 equiv of [(n-Bu)3(n-Pr)N]I and ammonium hexafluorophosphate to [(t-BuNC)(OC)3Mo(μ-dpm)2PdCl]Cl (6) yields golden brown [(t-BuNC)(OC)3Mo(μ-dpm)2PdI](PF6) (7). Orange-brown plates of [(t-BuNC)(OC)3Mo(μ-dpm)2PdI](PF6)· 0.5Et2O·H2O form in the tetragonal space group I42m with a = 22.822(4) A? and c = 27.013(7) A? at 130 K with Z = 8. Refinement of 3764 reflections and 388 parameters yielded R = 0.049 and Rw = 0.053. The structure consists of a seven-coordinate molybdenum atom with a nearly octahedral trans-P2Mo(CO)3(CNBu-t) core that is connected to a (P2PdI)+ unit through the two dpm bridges. The Mo-Pd bond length is 2.870(2) A?. Reaction of (t-BuNC)2PdCl2 and mer-Mo(dpm-P,P′)(dpm-P)(CO)3 in benzene yields dark brown crystals of (t-BuNC)-(OC)ClMo(μ-CO)(μ-dpm)2PdCl (8). Red-brown blocks of (t-BuNC)(OC)ClMo(μ-CO)(μ-dpm)2PdCl·2CHCl3 form in the monoclinic space group P21/c with a = 11.825(6) A?, b = 21.508(12) A?, c = 24.441(13) A?, and β = 100.77(4)° at 130 K with Z = 4. Refinement of 6413 reflections and 329 parameters yielded R = 0.069 and Rw = 0.061. This structure parallels the former with the exceptions that the terminal ligand bound to palladium is now a chloride ligand and one of the carbon monoxide ligands on molybdenum has been replaced by a terminal chloride ligand. The Mo-Pd bond length is 2.826(2) A?. The structure of the previously reported (OC)3(NC)Mo(μ-dpm)2Pd-(CN) has also been examined. (OC)3(NC)Mo(μ-dpm)2Pd(CN)·CH 3OH·0.5H2O crystallizes in the triclinic space group P1 with a =12.486(3) A?, b = 15.213(6) A?, c= 16.511(7) A?, α = 116.85(2)°, β = 96.17(2)°, and γ = 95.40(2)° at 130 K with Z = 2. Refinement of 4918 reflections and 268 parameters yielded R = 0.083 and Rw = 0.089. The structure consists of a trans-Mo(μ-dpm)2Pd core with three terminal carbonyl groups and a cyanide ligand bound to molybdenum and a terminal cyanide ligand attached to palladium. The Mo-Pd distance is 2.926(2) A?.
