Dinuclear [{(-C3H5)M(PR3)}2(
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- 作者：Davide Alberti ; Richard Goddard ; and Klaus-Richard Pö ; rschke
- 刊名：Organometallics
- 出版年：2005
- 出版时间：August 1, 2005
- 年：2005
- 卷：24
- 期：16
- 页码：3907 - 3915
- 全文大小：202K
- 年卷期：v.24,no.16(August 1, 2005)
- ISSN：1520-6041
文摘
The double halide-bridged 
-allyl complexes {(
3-C3H5)M(
-X)}2 (M = Ni, Pd; X = Cl, Br)resist halide abstraction by thallium salts of weakly coordinating anions Y = PF6, B(C6F5)4,and B{C6H3(CF3)2}4 in noncoordinating CH2Cl2. In the presence of a bulky phosphine(PiPr3, PtBu3) or when 2 equiv of (3-C3H5)M(PR3)X is reacted with TlY, one of the halideions is replaced to afford the ionic dinuclear, single halide-bridged complexes [{(3-C3H5)M(PR3)}2(-X)]Y (M = Ni, X = Br (6, 7); M = Pd, X = Cl (8, 9) and Br (10, 11)), which do notreact with further TlY. The corresponding complexes with Y = Al{OC(CF3)3}4 have also beenprepared. In addition, it has been found that the dinuclear palladium complexes, but notthe nickel derivatives, are also stable for Y = OTf. According to NMR the complexes representa mixture of diastereomers in solution. For [{(3-C3H5)Ni(PiPr3)}2(-Br)][Al{OC(CF3)3}4] (6c)and [{(3-C3H5)Pd(PtBu3)}2(-Br)][B(C6F5)4] (11b) the crystal structures have been determined. The reaction of (3-C3H5)M(PMe3)X with TlY affords a mixture of [(3-C3H5)M(PMe3)2]Y (described for M = Ni, Y = PF6 (12) and M = Pd, Y = PF6 (13)) and the startingphosphine-free {(3-C3H5)M(-X)}2.
-allyl complexes {(3-C3H5)M(-X)}2 (M = Ni, Pd; X = Cl, Br)resist halide abstraction by thallium salts of weakly coordinating anions Y = PF6, B(C6F5)4,and B{C6H3(CF3)2}4 in noncoordinating CH2Cl2. In the presence of a bulky phosphine(PiPr3, PtBu3) or when 2 equiv of (3-C3H5)M(PR3)X is reacted with TlY, one of the halideions is replaced to afford the ionic dinuclear, single halide-bridged complexes [{(3-C3H5)M(PR3)}2(-X)]Y (M = Ni, X = Br (6, 7); M = Pd, X = Cl (8, 9) and Br (10, 11)), which do notreact with further TlY. The corresponding complexes with Y = Al{OC(CF3)3}4 have also beenprepared. In addition, it has been found that the dinuclear palladium complexes, but notthe nickel derivatives, are also stable for Y = OTf. According to NMR the complexes representa mixture of diastereomers in solution. For [{(3-C3H5)Ni(PiPr3)}2(-Br)][Al{OC(CF3)3}4] (6c)and [{(3-C3H5)Pd(PtBu3)}2(-Br)][B(C6F5)4] (11b) the crystal structures have been determined. The reaction of (3-C3H5)M(PMe3)X with TlY affords a mixture of [(3-C3H5)M(PMe3)2]Y (described for M = Ni, Y = PF6 (12) and M = Pd, Y = PF6 (13)) and the startingphosphine-free {(3-C3H5)M(-X)}2.