Synthesis, structure and substitution reactions of the binuclear phosphido-bridged complex
Journal
Journal of Organometallic Chemistry
Journal Volume
489
Journal Issue
1-2
Pages
113-122
Date Issued
1995
Author(s)
Abstract
Bimetallic phosphido-bridged complexes CpW(CO)3(μ-PPh2)W(CO)5 (1) and CpW(CO)2(μ-PPh2W (Co)5 (2) were prepared by the reaction of CpW(CO)3PPh2 with W(CO)5THF. The structures of 1 and 2 were determined by single X-ray diffraction. Crystal data for 1: C25H15O8PW2, space group, P21/n with a = 9.6234 (18) A ̊, b = 12.4514 (20) A ̊, c = 20.750 (4) A ̊, β = 98.445 (14)°, V = 2459.4 (7) A ̊3, Z = 4. The structure was refined to R = 0.031 and RW = 0.035. Crystal data for 2: C24H15O7PW2, space group, P21/n with a = 14.4801 (11) A ̊, b = 11.6628 (12) A ̊, c = 14.732 (3) A ̊, β = 97.893 (11)°, V = 2464.3 (6) A ̊3, Z = 4. The structure was refined to R = 0.054 and RW = 0.050. The long distance between W and W (4.5096 (11) Å) in 1 indicates that no metal-metal bond exists in the complex. The W-W distance was 3.1942 (12) Å in 2, indicative of a W-W bond. Substitution reactions between 2 and Lewis bases L (L = PPh3, PEt3, P(OMe)3) produced CpW(CO)2(μ-PPh2W (CO)4(L) (3) with L regiospecifically and stereospecifically coordinating to the W(CO)4 moiety trans to the phosphido bridge. The structure of CpW(CO)2(μ-PPh2W(CO)4{P(OMe)3} (3a) was determined by single-crystal X-ray diffraction. Crystal data for 3a: C26H24O9P2W2, space group, P21 with a = 9.2231 (16) A ̊, b = 15.868 (3) A ̊, c = 10.745 (3) A ̊, β = 110.282 (18)°, V = 1475.1 (5) A ̊3, Z = 2. The structure was refined to R = 0.037 and RW = 0.039. Under similar reaction conditions, complex 1 did not react with L. © 1995.
Type
journal article