Issue 15, 2005
From the journal:

Dalton Transactions

Substitution, cage functionalization, and oxidation of the charge-compensated triruthenium monocarbollide cluster complex [1-SMe2-2,2-(CO)2-7,11-(μ-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H8]

Thomas D. McGrath,a   F. Gordon A. Stone*a  and  Kengkaj Sukcharoenphona  

* Corresponding authors

a Department of Chemistry and Biochemistry, Baylor University, Waco, Texas, USA

Abstract

The compound [1-SMe2-2,2-(CO)2-7,11-(μ-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H8] 1a reacts with PMe3 or PCy3 (Cy = cyclo-C6H11) to give the structurally different species [1-SMe2-2,2-(CO)2-7,11-(μ-H)2-2,7,11-{Ru2(CO)5(PMe3)}-closo-2,1-RuCB10H8] 4 and [1-SMe2-2,2-(CO)2-11-(μ-H)-2,7,11-{Ru2(μ-H)(CO)5(PCy3)}-closo-2,1-RuCB10H8] 5, respectively. A symmetrically disubstituted product [1-SMe2-2,2-(CO)2-7,11-(μ-H)2-2,7,11-{Ru2(CO)4(PMe3)2}-closo-2,1-RuCB10H8] 6 is obtained using an excess of PMe3. In contrast, the chelating diphosphines 1,1′-(PPh2)2-Fe(η-C5H4)2 and 1,2-(PPh2)2-closo-1,2-C2B10H10 react with 1a to yield oxidative-insertion species [1-SMe2-2,2-(CO)2-11-(μ-H)-2,7,11-{Ru2(μ-H)(μ-[1′,1″-(PPh2)2-Fe(η-C5H4)2])(CO)4}-closo-2,1-RuCB10H8] 7 and [1-SMe2-2,2-(CO)2-11-(μ-H)-2,7,11-{Ru2(μ-H)(CO)4(1′,2′-(PPh2)2-closo-1′,2′-C2B10H10)}-closo-2,1-RuCB10H8] 8, respectively. In toluene at reflux temperatures, 1a with ButSSBut gives [1-SMe2-2,2-(CO)2-7-(μ-SBut)-11-(μ-H)-2,7,11-{Ru2(μ-H)(μ-SBut)(CO)4}-closo-2,1-RuCB10H8] 9, and with ButC[triple bond, length as m-dash]CH gives [1-SMe2-2,2-(CO)2-7-{μ:η2-(E)–CH[double bond, length as m-dash]C(H)But}-11-{μ:η2-(E)–CH[double bond, length as m-dash]C(H)But}-2,7,11-{Ru2(CO)5}-closo-2,1-RuCB10H8] 10. In the latter, two alkyne groups have inserted into cage B–H groups, with one of the resulting B-vinyl moieties involved in a C–H⋯Ru agostic bond. Oxidation of 1a with I2 or HgCl2 affords the mononuclear ruthenium complex [1-SMe2-2,2,2-(CO)3-closo-2,1-RuCB10H10] 11.

Graphical abstract: Substitution, cage functionalization, and oxidation of the charge-compensated triruthenium monocarbollide cluster complex [1-SMe2-2,2-(CO)2-7,11-(μ-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H8]

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Article information

DOI
https://doi.org/10.1039/B505243B
Article type
Paper
Submitted
15 Apr 2005
Accepted
03 Jun 2005
First published
23 Jun 2005

Dalton Trans., 2005, 2500-2507

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Substitution, cage functionalization, and oxidation of the charge-compensated triruthenium monocarbollide cluster complex [1-SMe2-2,2-(CO)2-7,11-(μ-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H8]

T. D. McGrath, F. G. A. Stone and K. Sukcharoenphon, Dalton Trans., 2005, 2500 DOI: 10.1039/B505243B

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