Issue 21, 1999

Transition metal dicarbollide complexes: synthesis, molecular, crystal and electronic structures of [M(C2B9H11)(NMe2)3] (M = Nb or Ta) and their insertion reactions with CO2 and CS2

Abstract

The homoleptic amides [M(NMe2)5] (M = Nb 1 or Ta 2; the latter is characterised by a structural study) reacted with the carborane nido-C2B9H13 to eliminate two equivalents of HNMe2 and generate the dicarbollide half-sandwich tris(dimethylamide) complexes [M(C2B9H11)(NMe2)3] (M = Nb 3 or Ta 4). The crystal structures of isomorphous 3 and 4 have been determined and reveal two NMe2 ligands in a vertical orientation and the third one in a horizontal orientation with respect to the η5-co-ordinated face of the C2B9H11 ligand. The electronic factors responsible for the amide ligand orientations in these complexes are explored using qualitative MO arguments. Complexes 3 and 4 reacted with CO2 and CS2 to yield the tris(carbamate) [M(C2B9H11)(O2CNMe2)3] (M = Nb 5 or Ta 7) and tris(dithiocarbamate) [M(C2B9H11)(S2CNMe2)3] (M = Nb 6 or Ta 8) complexes, respectively. The crystal structures of 6 and 7 show two (dithio)carbamate ligands in horizontal and one in vertical orientation, demonstrating the similarity between the σ,π-donor frontier orbitals of the ligands NMe2 and X2CNMe2 in 4 and 6 or 7 respectively.

Supplementary files

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1999, 3867-3875

Transition metal dicarbollide complexes: synthesis, molecular, crystal and electronic structures of [M(C2B9H11)(NMe2)3] (M = Nb or Ta) and their insertion reactions with CO2 and CS2

A. S. Batsanov, A. V. Churakov, J. A. K. Howard, A. K. Hughes, A. L. Johnson, A. J. Kingsley, I. S. Neretin and K. Wade, J. Chem. Soc., Dalton Trans., 1999, 3867 DOI: 10.1039/A905075B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements