The homoleptic amides [M(NMe 2 ) 5 ] (M = Nb 1 or Ta 2; the latter is characterised by a structural study) reacted with the carborane nido-C 2 B 9 H 13 to eliminate two equivalents of HNMe 2 and generate the dicarbollide half-sandwich tris(dimethylamide) complexes [M(C 2 B 9 H 11 )(NMe 2 ) 3 ] (M = Nb 3 or Ta 4). The crystal structures of isomorphous 3 and 4 have been determined and reveal two NMe 2 ligands in a vertical orientation and the third one in a horizontal orientation with respect to the η 5 -co-ordinated face of the C 2 B 9 H 11 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 CO 2 and CS 2 to yield the tris(carbamateor 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 NMe 2 and X 2 CNMe 2 in 4 and 6 or 7 respectively.
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