摘要:
The reactivity of the d(8) transition metal complexes, [NiBr2(CH3OCH2CH2OCH3)] and MCl2L2 (M = Pd, Pt; L = CH3CN; L-2 = 1,5-cyclooctadiene), towards P(C6H5)(C6H4Cl-2)(2) (1) was investigated. While treatment of [PdCl2(cod)] with 2 equiv of 1 resulted in displacement of the weakly coordinating cyclooctadiene and formation of [PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)], analogous reactions with [PtCl2(cod)] afforded the monosubstituted species [PtCl2(cod)(P(C6H5)(C6H4Cl-2)(2))]. The disubstituted complex [PtCl2(P(C6H5)(C6H4Cl-2)(2))(2)] was successfully obtained by treatment of [PtCl2(NCCH3)(2)] with 2 equiv of 1. However, attempts to react I with [NiBr2(CH3OCH2CH2OCH3)] were unsuccessful. The chlorinated triphenyl phosphine is quite labile and is readily displaced from [PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)] by various Lewis bases including nitrogen containing ligands such as 2,2-bipyridine. The molecular structure of trans-[PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)] was determined by X-ray diffraction and represents the first molecular structure determination of a transition metal complex containing 1. This complex crystallizes in the monoclinic space group P2(1)/n with a = 10.3928(3) Angstrom, b = 16.0102(4) Angstrom, c = 13.1884(4) Angstrom, beta = 90.714(2)degrees, and Z = 4. Key geometric parameters include Pd-Cl(1) = 2.309(1) Angstrom, Pd-P(1) = 2.334(1) Angstrom,- Pd-P(1)-C(7) = 118.3(2)degrees, Pd-P(1)-C(1) = 115.3(2)degrees, C(1)-C(6)-Cl(2) = 120.7(4)degrees and Cl(1)-Pd-P(1) = 85.86(4)degrees. (C) 2002 Elsevier Science B.V. All rights reserved.