Issue 35, 2008

Ten-vertex polyhedral azametallaborane chemistry: a unique nido-6,9 to nido-6,8-clusterisomerization

Abstract

Reaction of the [arachno-4-NB8H12] anion 2 with [RhCl25-C5Me5)]2 in CH2Cl2 at room temperature affords a mixture of red ‘6,9’ isomer [9-(η5-C5Me5)-nido-6,9-NRhB8H11] (3) and its yellow ‘6,8’ isomer, [8-(η5-C5Me5)-nido-6,8-NRhB8H11] (4). Under the same conditions, reactions of 2 with [IrCl25-C5Me5)]2 and [RuCl26-MeC6H4-4-isoPr)]2 give the ‘6,8’ isomers, yellow [8-(η5-C5Me5)-nido-6,8-NIrB8H11] (5) and red [8-(η6-MeC6H4-4-isoPr)-nido-6,8-NRuB8H11] (6), respectively. In contrast, [IrCl(PPh3)3] yields orange [9,9-(PPh3)2-9-H-nido-6,9-NIrB8H11] (7), which exhibits the ‘6,9’ configuration. Compound 3 isomerizes quantitatively in solution to give 4. At high temperatures, compound 7 gives the yellow ‘6,8’ species, [8,8-(PPh3)2-8-H-nido-6,8-NIrB8H11] (8), in low yields. Possible mechanisms for the unprecedented 6,9 → 6,8 isomerization are discussed.

Graphical abstract: Ten-vertex polyhedral azametallaborane chemistry: a unique nido-6,9 to nido-6,8-cluster isomerization

Article information

Article type
Paper
Submitted
22 Apr 2008
Accepted
30 May 2008
First published
15 Jul 2008

Dalton Trans., 2008, 4776-4783

Ten-vertex polyhedral azametallaborane chemistry: a unique nido-6,9 to nido-6,8-cluster isomerization

R. Macías, J. Bould, J. Holub, B. Štíbr and J. D. Kennedy, Dalton Trans., 2008, 4776 DOI: 10.1039/B806784H

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