Ruthenium carbonyl cluster complexes with nitrogen ligands

Marie P. Cifuentes; Mark G. Humphrey; Brian W. Skelton; Allan H. White

doi:10.1016/0022-328X(94)88047-6

Ruthenium carbonyl cluster complexes with nitrogen ligands

Marie P. Cifuentes^*, Mark G. Humphrey, Brian W. Skelton, Allan H. White

^*Corresponding author for this work

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

22 Citations (Scopus)

Abstract

The reaction between Ru₃(μ-AuPPh₃)(μ-Cl)(CO)₁₀ (1) and pyridine afforded a mixture of products from which the title complexes Ru₃(μ-H)(μ-NC₅H₄)(CO)₉(PPh₃) (4), Ru₃ (μ-Cl)₂(CO)₈(NC₅H₅)(PPh₃) (6) and Ru₃(μ-Cl)₂(CO)₈(NC₅H₅)₂ (7) have been obtained together with the previously reported pyridyl cluster Ru₃(μ-H)(μ-NC₅H ₄)(CO)₁₀ (2) and the phosphine-substituted clusters Ru₃(CO)₁₀(PPh₃)₂ (3) and Ru₃(μ-Cl)₂(CO)₈(PPh₃)₂ (5). Complex 4 has also been obtained with a high yield by phosphine substitution of 2 under mild conditions. The structural study of 4 reveals site- specific substitution at the N-ligated ruthenium. Products 5-7 are dichloro-bridged complexes related by successive replacement of PPh₃ by NC₅H₅. Single-crystal X-ray diffraction studies of 6 and 7 indicate that these complexes contain triruthenium cores incorporating one and two σ-bound equatorially disposed pyridine ligands respectively, a new coordination mode for unsupported pyridine ligands on triruthenium clusters. Extremely long RuN distances in 6 and 7 are consistent with the "lightly stabilizing" nature of the pyridine ligand in trinuclear cluster chemistry. A comparison of the core geometries of 5-7 has revealed a contraction in the RuRu distances on sequential replacement of the P-donor ligand by the N-donor ligand.

Original language	English
Pages (from-to)	211-220
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	466
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(94)88047-6
Publication status	Published - 22 Feb 1994
Externally published	Yes

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@article{9f7b018aac414fb38b3cb4b8ec325d4e,

title = "Ruthenium carbonyl cluster complexes with nitrogen ligands",

abstract = "The reaction between Ru3(μ-AuPPh3)(μ-Cl)(CO)10 (1) and pyridine afforded a mixture of products from which the title complexes Ru3(μ-H)(μ-NC5H4)(CO)9(PPh3) (4), Ru3 (μ-Cl)2(CO)8(NC5H5)(PPh3) (6) and Ru3(μ-Cl)2(CO)8(NC5H5)2 (7) have been obtained together with the previously reported pyridyl cluster Ru3(μ-H)(μ-NC5H 4)(CO)10 (2) and the phosphine-substituted clusters Ru3(CO)10(PPh3)2 (3) and Ru3(μ-Cl)2(CO)8(PPh3)2 (5). Complex 4 has also been obtained with a high yield by phosphine substitution of 2 under mild conditions. The structural study of 4 reveals site- specific substitution at the N-ligated ruthenium. Products 5-7 are dichloro-bridged complexes related by successive replacement of PPh3 by NC5H5. Single-crystal X-ray diffraction studies of 6 and 7 indicate that these complexes contain triruthenium cores incorporating one and two σ-bound equatorially disposed pyridine ligands respectively, a new coordination mode for unsupported pyridine ligands on triruthenium clusters. Extremely long RuN distances in 6 and 7 are consistent with the {"}lightly stabilizing{"} nature of the pyridine ligand in trinuclear cluster chemistry. A comparison of the core geometries of 5-7 has revealed a contraction in the RuRu distances on sequential replacement of the P-donor ligand by the N-donor ligand.",

keywords = "Carbonyl, Crystal structure, Pyridine, Ruthenium",

author = "Cifuentes, {Marie P.} and Humphrey, {Mark G.} and Skelton, {Brian W.} and White, {Allan H.}",

year = "1994",

month = feb,

day = "22",

doi = "10.1016/0022-328X(94)88047-6",

language = "English",

volume = "466",

pages = "211--220",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

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TY - JOUR

T1 - Ruthenium carbonyl cluster complexes with nitrogen ligands

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

AU - Skelton, Brian W.

AU - White, Allan H.

PY - 1994/2/22

Y1 - 1994/2/22

N2 - The reaction between Ru3(μ-AuPPh3)(μ-Cl)(CO)10 (1) and pyridine afforded a mixture of products from which the title complexes Ru3(μ-H)(μ-NC5H4)(CO)9(PPh3) (4), Ru3 (μ-Cl)2(CO)8(NC5H5)(PPh3) (6) and Ru3(μ-Cl)2(CO)8(NC5H5)2 (7) have been obtained together with the previously reported pyridyl cluster Ru3(μ-H)(μ-NC5H 4)(CO)10 (2) and the phosphine-substituted clusters Ru3(CO)10(PPh3)2 (3) and Ru3(μ-Cl)2(CO)8(PPh3)2 (5). Complex 4 has also been obtained with a high yield by phosphine substitution of 2 under mild conditions. The structural study of 4 reveals site- specific substitution at the N-ligated ruthenium. Products 5-7 are dichloro-bridged complexes related by successive replacement of PPh3 by NC5H5. Single-crystal X-ray diffraction studies of 6 and 7 indicate that these complexes contain triruthenium cores incorporating one and two σ-bound equatorially disposed pyridine ligands respectively, a new coordination mode for unsupported pyridine ligands on triruthenium clusters. Extremely long RuN distances in 6 and 7 are consistent with the "lightly stabilizing" nature of the pyridine ligand in trinuclear cluster chemistry. A comparison of the core geometries of 5-7 has revealed a contraction in the RuRu distances on sequential replacement of the P-donor ligand by the N-donor ligand.

AB - The reaction between Ru3(μ-AuPPh3)(μ-Cl)(CO)10 (1) and pyridine afforded a mixture of products from which the title complexes Ru3(μ-H)(μ-NC5H4)(CO)9(PPh3) (4), Ru3 (μ-Cl)2(CO)8(NC5H5)(PPh3) (6) and Ru3(μ-Cl)2(CO)8(NC5H5)2 (7) have been obtained together with the previously reported pyridyl cluster Ru3(μ-H)(μ-NC5H 4)(CO)10 (2) and the phosphine-substituted clusters Ru3(CO)10(PPh3)2 (3) and Ru3(μ-Cl)2(CO)8(PPh3)2 (5). Complex 4 has also been obtained with a high yield by phosphine substitution of 2 under mild conditions. The structural study of 4 reveals site- specific substitution at the N-ligated ruthenium. Products 5-7 are dichloro-bridged complexes related by successive replacement of PPh3 by NC5H5. Single-crystal X-ray diffraction studies of 6 and 7 indicate that these complexes contain triruthenium cores incorporating one and two σ-bound equatorially disposed pyridine ligands respectively, a new coordination mode for unsupported pyridine ligands on triruthenium clusters. Extremely long RuN distances in 6 and 7 are consistent with the "lightly stabilizing" nature of the pyridine ligand in trinuclear cluster chemistry. A comparison of the core geometries of 5-7 has revealed a contraction in the RuRu distances on sequential replacement of the P-donor ligand by the N-donor ligand.

KW - Carbonyl

KW - Crystal structure

KW - Pyridine

KW - Ruthenium

UR - http://www.scopus.com/inward/record.url?scp=0001766544&partnerID=8YFLogxK

U2 - 10.1016/0022-328X(94)88047-6

DO - 10.1016/0022-328X(94)88047-6

M3 - Article

AN - SCOPUS:0001766544

SN - 0022-328X

VL - 466

SP - 211

EP - 220

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Ruthenium carbonyl cluster complexes with nitrogen ligands

Abstract

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