High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters

Michael D. Randles; Marie P. Cifuentes; Graeme J. Moxey; Achim Zahl; Rudi van Eldik; Mark G. Humphrey

doi:10.1016/j.jorganchem.2017.05.026

High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters

Michael D. Randles, Marie P. Cifuentes, Graeme J. Moxey, Achim Zahl, Rudi van Eldik, Mark G. Humphrey^*

^*Corresponding author for this work

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

2 Citations (Scopus)

Abstract

The mono- to tri-substituted decaruthenium cluster anions [Ru₁₀(μ-H)(μ₆-C)(CO)_24–x(L)_x]^- [L = P(C₆H₄Me-4)₃, AsPh₃, SbPh₃, x = 1–3] were prepared as their [PPh₄]⁺ salts in moderate to good yields from reaction of [PPh₄][Ru₁₀(μ-H)(μ₆-C)(CO)₂₄] with the corresponding group 15 ligands at room temperature in acetone. The tetrakis-substituted cluster Ru₁₀(μ₆-C)(μ₃-CO)(μ-CO)(CO)₁₉{P(C₆H₄Me-4)₃}₄ was obtained in high yield from [PPh₄]₂[Ru₁₀(μ₆–C)(CO)₂₄] and an excess of the phosphine under the same conditions; a single-crystal X-ray diffraction study revealed that the phosphines ligate at the vertices of the “giant tetrahedral” core. Kinetics studies of the formation of [PPh₄][Ru₁₀(μ-H)(μ₆-C)(AsPh₃)₂(CO)₂₂] from [PPh₄][Ru₁₀(μ-H)(μ₆-C)(AsPh₃)(CO)₂₃] shows that ligand substitution at these giant tetrahedral clusters proceeds via a strongly associative pathway with the likely intermediacy of a Ru-Ru bond-cleaved intermediate.

Original language	English
Pages (from-to)	63-70
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	849-850
DOIs	https://doi.org/10.1016/j.jorganchem.2017.05.026
Publication status	Published - 1 Nov 2017

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@article{3d662af493df4d349f60fecb375dd169,

title = "High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters",

abstract = "The mono- to tri-substituted decaruthenium cluster anions [Ru10(μ-H)(μ6-C)(CO)24–x(L)x]- [L = P(C6H4Me-4)3, AsPh3, SbPh3, x = 1–3] were prepared as their [PPh4]+ salts in moderate to good yields from reaction of [PPh4][Ru10(μ-H)(μ6-C)(CO)24] with the corresponding group 15 ligands at room temperature in acetone. The tetrakis-substituted cluster Ru10(μ6-C)(μ3-CO)(μ-CO)(CO)19{P(C6H4Me-4)3}4 was obtained in high yield from [PPh4]2[Ru10(μ6–C)(CO)24] and an excess of the phosphine under the same conditions; a single-crystal X-ray diffraction study revealed that the phosphines ligate at the vertices of the “giant tetrahedral” core. Kinetics studies of the formation of [PPh4][Ru10(μ-H)(μ6-C)(AsPh3)2(CO)22] from [PPh4][Ru10(μ-H)(μ6-C)(AsPh3)(CO)23] shows that ligand substitution at these giant tetrahedral clusters proceeds via a strongly associative pathway with the likely intermediacy of a Ru-Ru bond-cleaved intermediate.",

keywords = "High-nuclearity clusters, Kinetics, Ruthenium, X-ray structure",

author = "Randles, {Michael D.} and Cifuentes, {Marie P.} and Moxey, {Graeme J.} and Achim Zahl and {van Eldik}, Rudi and Humphrey, {Mark G.}",

note = "Publisher Copyright: {\textcopyright} 2017 Elsevier B.V.",

year = "2017",

month = nov,

day = "1",

doi = "10.1016/j.jorganchem.2017.05.026",

language = "English",

volume = "849-850",

pages = "63--70",

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T1 - High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters

AU - Randles, Michael D.

AU - Cifuentes, Marie P.

AU - Moxey, Graeme J.

AU - Zahl, Achim

AU - van Eldik, Rudi

AU - Humphrey, Mark G.

PY - 2017/11/1

Y1 - 2017/11/1

N2 - The mono- to tri-substituted decaruthenium cluster anions [Ru10(μ-H)(μ6-C)(CO)24–x(L)x]- [L = P(C6H4Me-4)3, AsPh3, SbPh3, x = 1–3] were prepared as their [PPh4]+ salts in moderate to good yields from reaction of [PPh4][Ru10(μ-H)(μ6-C)(CO)24] with the corresponding group 15 ligands at room temperature in acetone. The tetrakis-substituted cluster Ru10(μ6-C)(μ3-CO)(μ-CO)(CO)19{P(C6H4Me-4)3}4 was obtained in high yield from [PPh4]2[Ru10(μ6–C)(CO)24] and an excess of the phosphine under the same conditions; a single-crystal X-ray diffraction study revealed that the phosphines ligate at the vertices of the “giant tetrahedral” core. Kinetics studies of the formation of [PPh4][Ru10(μ-H)(μ6-C)(AsPh3)2(CO)22] from [PPh4][Ru10(μ-H)(μ6-C)(AsPh3)(CO)23] shows that ligand substitution at these giant tetrahedral clusters proceeds via a strongly associative pathway with the likely intermediacy of a Ru-Ru bond-cleaved intermediate.

AB - The mono- to tri-substituted decaruthenium cluster anions [Ru10(μ-H)(μ6-C)(CO)24–x(L)x]- [L = P(C6H4Me-4)3, AsPh3, SbPh3, x = 1–3] were prepared as their [PPh4]+ salts in moderate to good yields from reaction of [PPh4][Ru10(μ-H)(μ6-C)(CO)24] with the corresponding group 15 ligands at room temperature in acetone. The tetrakis-substituted cluster Ru10(μ6-C)(μ3-CO)(μ-CO)(CO)19{P(C6H4Me-4)3}4 was obtained in high yield from [PPh4]2[Ru10(μ6–C)(CO)24] and an excess of the phosphine under the same conditions; a single-crystal X-ray diffraction study revealed that the phosphines ligate at the vertices of the “giant tetrahedral” core. Kinetics studies of the formation of [PPh4][Ru10(μ-H)(μ6-C)(AsPh3)2(CO)22] from [PPh4][Ru10(μ-H)(μ6-C)(AsPh3)(CO)23] shows that ligand substitution at these giant tetrahedral clusters proceeds via a strongly associative pathway with the likely intermediacy of a Ru-Ru bond-cleaved intermediate.

KW - High-nuclearity clusters

KW - Kinetics

KW - Ruthenium

KW - X-ray structure

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U2 - 10.1016/j.jorganchem.2017.05.026

DO - 10.1016/j.jorganchem.2017.05.026

M3 - Article

SN - 0022-328X

VL - 849-850

SP - 63

EP - 70

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters

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