862889-63-2Relevant academic research and scientific papers
Dinuclear [{(π-C3H5)M(PR3)} 2(μ-X)]Y complexes of nickel and palladium
Alberti, Davide,Goddard, Richard,Poerschke, Klaus-Richard
, p. 3907 - 3915 (2008/10/09)
The double halide-bridged π-allyl complexes {(η3-C 3H5)M(μ-X)}2 (M = Ni, Pd; X = Cl, Br) resist halide abstraction by thallium salts of weakly coordinating anions Y = PF 6, B(C6F5)4, and B{C 6H3(CF3)2}4 in noncoordinating CH2Cl2. In the presence of a bulky phosphine (PiPr3, PtBu3) or when 2 equiv of (η3-C3H5)M(PR3)X is reacted with TlY, one of the halide ions is replaced to afford the ionic dinuclear, single halide-bridged complexes [{(η3-C 3H5)M-(PR3)}2(μ-X)]Y (M = Ni, X = Br (6, 7); M - Pd, X = Cl (8, 9) and Br (10, 11)), which do not react with further TlY. The corresponding complexes with Y = Al{OC(CF3) 3}4 have also been prepared. In addition, it has been found that the dinuclear palladium complexes, but not the nickel derivatives, are also stable for Y = OTf. According to NMR the complexes represent a mixture of diastereomers in solution. For [{(η3-C3H 5)Ni(PiPr3)}2(μ-Br)] [Al{OC(CF3)3}4] (6c) and [{(η3- C3H5)Pd(PtBu3)}2(μ-Br) ][B(C6F5)4] (11b) the crystal structures have been determined. The reaction of (η3-C3H 5)M(PMe3)X with TlY affords a mixture of [(η3-C3H5)M-(PMe3) 2]Y (described for M = Ni, Y = PF6 (12) and M - Pd, Y = PF6 (13)) and the starting phosphine-free {(η3-C 3H5)M(μ-X)}2.
