Diphenylphosphinoacetate, nicotinate and thiophenoxyacetate as bridging ligands in heterometallic complexes involving bis(η-cyclopentadienyl)titanium(IV) and group 10 or 11 metal chlorides.
摘要:
Heterobi- and tri-metallic compounds containing a Cp2Ti(IV) unit linked via nicotinate, thiophenoxyacetate or diphenylphosphinoacetate ligands to Pd, Pt, Cu, Ag or An centres have been isolated. They are of the types [Cp2Ti{mu-OC(O)R}(2)MCl2] (M = Pd, R = m-C5H4N, CH2SPh and CH2PPh2; M = Pt, R = m-C5H4N or CH2PPh2), [Cp2Ti{mu-OC(O)CH2PPh2}(2)( M'Cl)(2)] (M' = Cu or Au) and [Cp2Ti{mu-OC(O)CH2PPh2}(2)AgCl]. The diphenylphosphinoacetate products arise both from methane elimination reactions of [Cp2TiMe2] with either [MCl2(Ph2PCH2CO2H)(2)] or [M'Cl(Ph2PCH2CO2H)] and from reactions of [Cp2Ti{mu-OC(O)CH2PPh2}(2)] with metal complexes containing labile ligands. Crystal structures of [Cp2Ti{OC(O)CH2PPh2}(2)] and [Cp2Ti{mu-OC(O)CH2PPh2}(2)PdCl2] are discussed. The latter compound contains diphenylphosphinoacetate groups which are O-unidentate with respect to titanium and P-unidentate with respect to palladium, the result being the formation of a ten-atom heterobimetallic ring system. (C) 2000 Elsevier Science Ltd All rights reserved.
Some metal complexes containing diphenylphosphinoacetic acid as a P-bonded neutral ligand. Crystal structures of [AuCl(Ph2PCH2CO2H)] and trans- [PdCl2(Ph2PCH2CO2H)2]0.33H2O · 0.33C2H5OH
摘要:
Diphenylphosphinoacetic acid (HA) reacts as a neutral P-donor ligand with a variety of transition metal compounds to generate the new complexes [CuCl(HA)(x)] (x = 1 or 3), trans-[PdCl2(HA)(2)], cis-[PtCl2(HA)(2)], [AuCl(HA)] and cis-[Mo(CO)(4)(HA)(2)]. The crystal structure of [AuCI(HA)] involves a linear Cl-Au-P arrange ment [179.0(1)degrees], neighbouring molecules forming hydrogen-bonded dimers in the lattice array. The hydrogen-bonding is of the planar type commonly found in free carboxylic acids with intermolecularly bonded pairs of [AuCl(HA)] molecules being related by an inversion centre. Recrystallisation of trans-[PdCl2(HA)(2)] from ethanol yields crystals of the solvate trans-[PdCl2(HA)(2)]. 0.33H(2)O . 0.33C(2)H(5)OH. The asymmetric unit contains 1.5[PdCl2(HA)(2)] molecules along with water and ethanol molecules exhibiting only half site occupancy. For every three [PdCl2(HA)(2)] molecules two are hydrogen-bonded to neighbours using carboxylic acid groups to form chains. The third molecule differs in that hydrogen-bonding occurs between one oxygen of a carboxylic acid group and the lattice water, the oxygen of which further hydrogen-bonds to the lattice ethanol. (C) 1998 Elsevier Science Ltd. All rights reserved.