Mixed-metal cluster chemistry 15: Some bidentate phosphine chemistry of tungsten-iridium clusters

Susan M. Waterman; Mark G. Humphrey; Jeanne Lee

doi:10.1016/S0022-328X(99)00406-4

Mixed-metal cluster chemistry 15: Some bidentate phosphine chemistry of tungsten-iridium clusters

Susan M. Waterman^*, Mark G. Humphrey, Jeanne Lee

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

Reactions of [Cp₂W₂Ir₂(CO)₁₀] (4) with equimolar amounts of the bidentate phosphines bis(diphenylphosphino)methane (dppm) and 1,2-bis(diphenylphosphino)ethane (dppe) afford the substitution products [Cp₂W₂Ir₂(μ-CO)₃(μ-L)(CO) ₅] [L=dppm (5), dppe (6)] in excellent yields (76% and 80%, respectively). The clusters 5 and 6 are fluxional in solution, with the interconverting isomers of 6 resolvable at low temperatures. Variable-temperature ³¹P- and ¹³C-NMR for 5 and 6 enable structural assignment of the isomers. ¹³C-NMR exchange spectroscopy (EXSY) spectra reveal that the fluxional process observed with 5, and which interconverts the isomers of 6, involves a 'waggling' of the CpW(CO)₂ group over the W₂Ir faces or complete tripodal rotation at the apical CpW(CO)₂. Reaction of [CpWIr₃(CO)₁₁] (1) with an equimolar amount of the bidentate phosphine 1,2-bis(diphenylphosphino)benzene (pdpp) affords the substitution product [CpWIr₃(μ-CO)₃(μ-pdpp)(CO)₆] (7) in reasonable yield (62%). Spectroscopic data suggest 7 adopts one configuration in solution, in contrast to the two configurations observed with [CpWIr₃(μ-CO)₃(μ-L)(CO)₆] [L=dppe (2), dppm (3)], a result ascribed to the inflexible diphosphine backbone.

Original language	English
Pages (from-to)	226-233
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	589
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(99)00406-4
Publication status	Published - 5 Nov 1999

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10.1016/S0022-328X(99)00406-4

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@article{071d3a1361e748498519ae88b11433b8,

title = "Mixed-metal cluster chemistry 15: Some bidentate phosphine chemistry of tungsten-iridium clusters",

abstract = "Reactions of [Cp2W2Ir2(CO)10] (4) with equimolar amounts of the bidentate phosphines bis(diphenylphosphino)methane (dppm) and 1,2-bis(diphenylphosphino)ethane (dppe) afford the substitution products [Cp2W2Ir2(μ-CO)3(μ-L)(CO) 5] [L=dppm (5), dppe (6)] in excellent yields (76% and 80%, respectively). The clusters 5 and 6 are fluxional in solution, with the interconverting isomers of 6 resolvable at low temperatures. Variable-temperature 31P- and 13C-NMR for 5 and 6 enable structural assignment of the isomers. 13C-NMR exchange spectroscopy (EXSY) spectra reveal that the fluxional process observed with 5, and which interconverts the isomers of 6, involves a 'waggling' of the CpW(CO)2 group over the W2Ir faces or complete tripodal rotation at the apical CpW(CO)2. Reaction of [CpWIr3(CO)11] (1) with an equimolar amount of the bidentate phosphine 1,2-bis(diphenylphosphino)benzene (pdpp) affords the substitution product [CpWIr3(μ-CO)3(μ-pdpp)(CO)6] (7) in reasonable yield (62%). Spectroscopic data suggest 7 adopts one configuration in solution, in contrast to the two configurations observed with [CpWIr3(μ-CO)3(μ-L)(CO)6] [L=dppe (2), dppm (3)], a result ascribed to the inflexible diphosphine backbone.",

keywords = "Carbonyl, Cluster, Cyclopentadienyl, Fluxionality, Iridium, Phosphine, Tungsten",

author = "Waterman, {Susan M.} and Humphrey, {Mark G.} and Jeanne Lee",

year = "1999",

month = nov,

day = "5",

doi = "10.1016/S0022-328X(99)00406-4",

language = "English",

volume = "589",

pages = "226--233",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "2",

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TY - JOUR

T1 - Mixed-metal cluster chemistry 15

T2 - Some bidentate phosphine chemistry of tungsten-iridium clusters

AU - Waterman, Susan M.

AU - Humphrey, Mark G.

AU - Lee, Jeanne

PY - 1999/11/5

Y1 - 1999/11/5

N2 - Reactions of [Cp2W2Ir2(CO)10] (4) with equimolar amounts of the bidentate phosphines bis(diphenylphosphino)methane (dppm) and 1,2-bis(diphenylphosphino)ethane (dppe) afford the substitution products [Cp2W2Ir2(μ-CO)3(μ-L)(CO) 5] [L=dppm (5), dppe (6)] in excellent yields (76% and 80%, respectively). The clusters 5 and 6 are fluxional in solution, with the interconverting isomers of 6 resolvable at low temperatures. Variable-temperature 31P- and 13C-NMR for 5 and 6 enable structural assignment of the isomers. 13C-NMR exchange spectroscopy (EXSY) spectra reveal that the fluxional process observed with 5, and which interconverts the isomers of 6, involves a 'waggling' of the CpW(CO)2 group over the W2Ir faces or complete tripodal rotation at the apical CpW(CO)2. Reaction of [CpWIr3(CO)11] (1) with an equimolar amount of the bidentate phosphine 1,2-bis(diphenylphosphino)benzene (pdpp) affords the substitution product [CpWIr3(μ-CO)3(μ-pdpp)(CO)6] (7) in reasonable yield (62%). Spectroscopic data suggest 7 adopts one configuration in solution, in contrast to the two configurations observed with [CpWIr3(μ-CO)3(μ-L)(CO)6] [L=dppe (2), dppm (3)], a result ascribed to the inflexible diphosphine backbone.

AB - Reactions of [Cp2W2Ir2(CO)10] (4) with equimolar amounts of the bidentate phosphines bis(diphenylphosphino)methane (dppm) and 1,2-bis(diphenylphosphino)ethane (dppe) afford the substitution products [Cp2W2Ir2(μ-CO)3(μ-L)(CO) 5] [L=dppm (5), dppe (6)] in excellent yields (76% and 80%, respectively). The clusters 5 and 6 are fluxional in solution, with the interconverting isomers of 6 resolvable at low temperatures. Variable-temperature 31P- and 13C-NMR for 5 and 6 enable structural assignment of the isomers. 13C-NMR exchange spectroscopy (EXSY) spectra reveal that the fluxional process observed with 5, and which interconverts the isomers of 6, involves a 'waggling' of the CpW(CO)2 group over the W2Ir faces or complete tripodal rotation at the apical CpW(CO)2. Reaction of [CpWIr3(CO)11] (1) with an equimolar amount of the bidentate phosphine 1,2-bis(diphenylphosphino)benzene (pdpp) affords the substitution product [CpWIr3(μ-CO)3(μ-pdpp)(CO)6] (7) in reasonable yield (62%). Spectroscopic data suggest 7 adopts one configuration in solution, in contrast to the two configurations observed with [CpWIr3(μ-CO)3(μ-L)(CO)6] [L=dppe (2), dppm (3)], a result ascribed to the inflexible diphosphine backbone.

KW - Carbonyl

KW - Cluster

KW - Cyclopentadienyl

KW - Fluxionality

KW - Iridium

KW - Phosphine

KW - Tungsten

UR - http://www.scopus.com/inward/record.url?scp=0001219035&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(99)00406-4

DO - 10.1016/S0022-328X(99)00406-4

M3 - Article

SN - 0022-328X

VL - 589

SP - 226

EP - 233

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2

ER -

Mixed-metal cluster chemistry 15: Some bidentate phosphine chemistry of tungsten-iridium clusters

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