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

Randles MD, Cifuentes MP, Moxey GJ, Zahl A, van Eldik R, Humphrey MG (2017)


Publication Status: Published

Publication Type: Journal article

Publication year: 2017

Journal

Publisher: ELSEVIER SCIENCE SA

Book Volume: 849-850

Pages Range: 63-70

DOI: 10.1016/j.jorganchem.2017.05.026

Abstract

The mono-to tri-substituted decaruthenium cluster anions [Ru-10(mu-H)(mu(6)-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][Ru-10(mu-H)(mu(6)-C)(CO)(24)] with the corresponding group 15 ligands at room temperature in acetone. The tetrakis-substituted cluster Ru-10(mu(6)-C)(mu(3)-CO)(mu-CO)(CO)(19){P(C6H4Me-4)(3)}(4) was obtained in high yield from [PPh4](2)[Ru-10(mu(6)-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][Ru-10(mu-H)(mu(6)-C)(AsPh3)(2)(CO)(22)] from [PPh4][Ru-10(mu-H)(mu(6)-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. (C) 2017 Elsevier B.V. All rights reserved.

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How to cite

APA:

Randles, M.D., Cifuentes, M.P., Moxey, G.J., Zahl, A., van Eldik, R., & Humphrey, M.G. (2017). High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters. Journal of Organometallic Chemistry, 849-850, 63-70. https://dx.doi.org/10.1016/j.jorganchem.2017.05.026

MLA:

Randles, Michael D., et al. "High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters." Journal of Organometallic Chemistry 849-850 (2017): 63-70.

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