Mixed-metal cluster chemistry III . P-C activation at tungsten-triiridium cores; X-ray crystal structures of [CpWIr3 {μ3-η2-PPh(C6H4)} (μ-CO)2(CO) 7]

Susan M. Waterman; Vicki Anne Tolhurst; Mark G. Humphrey; Brian W. Skelton; Allan H. White

doi:10.1016/0022-328X(95)06070-D

Mixed-metal cluster chemistry III . P-C activation at tungsten-triiridium cores; X-ray crystal structures of [CpWIr₃ {μ₃-η²-PPh(C₆H₄)} (μ-CO)₂(CO) ₇]

Susan M. Waterman, Vicki Anne Tolhurst, Mark G. Humphrey^*, Brian W. Skelton, Allan H. White

^*Corresponding author for this work

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Abstract

The thermolysis of [CpWIr₃(μ-CO)₃(CO)₇(PPh₃)] in refluxing toluene gives [CpWIr₃{μ₃-η²-PPh(C₆H₄)}(μ-CO)₂(CO)₇] (1) in good yield (56%), together with [CpWIr3(CO)₁₁] (2) (32%); an analogous reaction with [CpWIr₃(μ-CO)₃(CO)₆(PPh₃)₂] gives 1 (23%) and [CpWIr₃{μ₃-η²-PPh(C₆H₄)}(μ-CO)₂(CO)₆(PPh₃)] (3) (39%). Products 1 and 3 (in 15 and 44% yield respectively) are also obtained from heating [CpWIr₃(μ-CO)₃(CO)₅(PPh₃)₃]. Both 1 and 3 have been structurally characterized. The structural studies show that orthometallation has occurred, to afford products with (phenylphosphido)phenyl-P,C ligands capping the triiridium faces. In 3, the intact PPh₃ resides at an iridium ligated by the phosphorus of the capping group. Attempts to effect further P-C cleavage of 1 (pyrolysis, photolysis, reaction with trimethylamine-N-oxide) were unsuccessful, as were attempts to effect C-H activation at the analogous [CpWIr₃(μ-CO)₃(CO)₇(PMe₃)].

Original language	English
Pages (from-to)	89-98
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	515
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(95)06070-D
Publication status	Published - 31 May 1996

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@article{8d859e5f8d6b4fdbb16917d48476b2ae,

title = "Mixed-metal cluster chemistry III . P-C activation at tungsten-triiridium cores; X-ray crystal structures of [CpWIr3 {μ3-η2-PPh(C6H4)} (μ-CO)2(CO) 7]",

abstract = "The thermolysis of [CpWIr3(μ-CO)3(CO)7(PPh3)] in refluxing toluene gives [CpWIr3{μ3-η2-PPh(C6H4)}(μ-CO)2(CO)7] (1) in good yield (56%), together with [CpWIr3(CO)11] (2) (32%); an analogous reaction with [CpWIr3(μ-CO)3(CO)6(PPh3)2] gives 1 (23%) and [CpWIr3{μ3-η2-PPh(C6H4)}(μ-CO)2(CO)6(PPh3)] (3) (39%). Products 1 and 3 (in 15 and 44% yield respectively) are also obtained from heating [CpWIr3(μ-CO)3(CO)5(PPh3)3]. Both 1 and 3 have been structurally characterized. The structural studies show that orthometallation has occurred, to afford products with (phenylphosphido)phenyl-P,C ligands capping the triiridium faces. In 3, the intact PPh3 resides at an iridium ligated by the phosphorus of the capping group. Attempts to effect further P-C cleavage of 1 (pyrolysis, photolysis, reaction with trimethylamine-N-oxide) were unsuccessful, as were attempts to effect C-H activation at the analogous [CpWIr3(μ-CO)3(CO)7(PMe3)].",

keywords = "Cluster, Crystal structure, Iridium, Orthometallation, Tungsten",

author = "Waterman, {Susan M.} and Tolhurst, {Vicki Anne} and Humphrey, {Mark G.} and Skelton, {Brian W.} and White, {Allan H.}",

year = "1996",

month = may,

day = "31",

doi = "10.1016/0022-328X(95)06070-D",

language = "English",

volume = "515",

pages = "89--98",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

Mixed-metal cluster chemistry III . P-C activation at tungsten-triiridium cores; X-ray crystal structures of [CpWIr₃ {μ₃-η²-PPh(C₆H₄)} (μ-CO)₂(CO) ₇]. / Waterman, Susan M.; Tolhurst, Vicki Anne; Humphrey, Mark G. et al.
In: Journal of Organometallic Chemistry, Vol. 515, No. 1-2, 31.05.1996, p. 89-98.

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

TY - JOUR

T1 - Mixed-metal cluster chemistry III . P-C activation at tungsten-triiridium cores; X-ray crystal structures of [CpWIr3 {μ3-η2-PPh(C6H4)} (μ-CO)2(CO) 7]

AU - Waterman, Susan M.

AU - Tolhurst, Vicki Anne

AU - Humphrey, Mark G.

AU - Skelton, Brian W.

AU - White, Allan H.

PY - 1996/5/31

Y1 - 1996/5/31

N2 - The thermolysis of [CpWIr3(μ-CO)3(CO)7(PPh3)] in refluxing toluene gives [CpWIr3{μ3-η2-PPh(C6H4)}(μ-CO)2(CO)7] (1) in good yield (56%), together with [CpWIr3(CO)11] (2) (32%); an analogous reaction with [CpWIr3(μ-CO)3(CO)6(PPh3)2] gives 1 (23%) and [CpWIr3{μ3-η2-PPh(C6H4)}(μ-CO)2(CO)6(PPh3)] (3) (39%). Products 1 and 3 (in 15 and 44% yield respectively) are also obtained from heating [CpWIr3(μ-CO)3(CO)5(PPh3)3]. Both 1 and 3 have been structurally characterized. The structural studies show that orthometallation has occurred, to afford products with (phenylphosphido)phenyl-P,C ligands capping the triiridium faces. In 3, the intact PPh3 resides at an iridium ligated by the phosphorus of the capping group. Attempts to effect further P-C cleavage of 1 (pyrolysis, photolysis, reaction with trimethylamine-N-oxide) were unsuccessful, as were attempts to effect C-H activation at the analogous [CpWIr3(μ-CO)3(CO)7(PMe3)].

AB - The thermolysis of [CpWIr3(μ-CO)3(CO)7(PPh3)] in refluxing toluene gives [CpWIr3{μ3-η2-PPh(C6H4)}(μ-CO)2(CO)7] (1) in good yield (56%), together with [CpWIr3(CO)11] (2) (32%); an analogous reaction with [CpWIr3(μ-CO)3(CO)6(PPh3)2] gives 1 (23%) and [CpWIr3{μ3-η2-PPh(C6H4)}(μ-CO)2(CO)6(PPh3)] (3) (39%). Products 1 and 3 (in 15 and 44% yield respectively) are also obtained from heating [CpWIr3(μ-CO)3(CO)5(PPh3)3]. Both 1 and 3 have been structurally characterized. The structural studies show that orthometallation has occurred, to afford products with (phenylphosphido)phenyl-P,C ligands capping the triiridium faces. In 3, the intact PPh3 resides at an iridium ligated by the phosphorus of the capping group. Attempts to effect further P-C cleavage of 1 (pyrolysis, photolysis, reaction with trimethylamine-N-oxide) were unsuccessful, as were attempts to effect C-H activation at the analogous [CpWIr3(μ-CO)3(CO)7(PMe3)].

KW - Cluster

KW - Crystal structure

KW - Iridium

KW - Orthometallation

KW - Tungsten

UR - http://www.scopus.com/inward/record.url?scp=0030607966&partnerID=8YFLogxK

U2 - 10.1016/0022-328X(95)06070-D

DO - 10.1016/0022-328X(95)06070-D

M3 - Article

AN - SCOPUS:0030607966

SN - 0022-328X

VL - 515

SP - 89

EP - 98

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Mixed-metal cluster chemistry III . P-C activation at tungsten-triiridium cores; X-ray crystal structures of [CpWIr₃ {μ₃-η²-PPh(C₆H₄)} (μ-CO)₂(CO) ₇]

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