Mixed-Metal Cluster Chemistry. Site-Selective Reactions of CpWIr3(CO)11 with PPh3 and Bidentate Phosphines: X-ray Crystal Structures of CpWIr3(µ-dppe)(µ-CO)3(CO)6, CpWIr3(µ-dppm)(µ-CO)3(CO)6, and CpWIr3(µ-dppa)(µ-CO)3(CO)6

Jeanne Lee, Mark G. Humphrey*, David C.R. Hockless, Brian W. Skelton, Allan H. White

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

36 Citations (Scopus)

Abstract

Reactions of CpWIr3(CO)11 (1) with equimolar amounts of phosphines afford the site-selective monophosphine cluster products CpWIr3(µ-CO)3(CO)8−x(L) (L = PPh3 (2a), x = 1; L = µ-dppe (2b), µ-dppm (2c), x = 2) in excellent yields (64–84%). Reaction of 1 with the linear diphosphine dppa, Ph2PC≡CPPh2, affords CpWIr3(µ-dppa)(µ-CO)3(CO)6 (2d) in low yield (15%). From the 31P NMR spectrum and preliminary crystallographic results, PPh3 has been assigned to a radial site in 2a. The structures of 2b, 2c, and 2d have been determined by single crystal X-ray diffraction studies; in these three cases, the bidentate phosphines are diaxially-coordinated. In 2d, the bidentate phosphine is highly strained, with an ∠PC≡C of 147.2(8)°. Crystal data: for 2b, space group = P1̅, a = 18.563(5) Å, b = 11.855(4) Å, c = 10.367(2) Å, a = 67.72(2)°, β = 73.54(2)°, γ = 77.44(2)°, Z = 2, No = 10 230 “observed” reflections (I > 3σ-(I)), R = 0.045; for 2c, space group = P21/c, a = 10.748(12) Å, b = 22.439(5) Å, c = 19.886(14) Å, β = 114.95(8)°, Z = 4, No = 2710, R = 0.087; for 2d, space group = Pmnb, a = 21.608(4) Å, b = 17.843(3) Å, c = 10.134(3) Å, Z = 4,No = 2740, R = 0.032.

Original languageEnglish
Pages (from-to)3468-3473
Number of pages6
JournalOrganometallics
Volume12
Issue number9
DOIs
Publication statusPublished - 1993
Externally publishedYes

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