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Synthesis and Characterisation of Sigma‐ and Pi‐Bonded Metallaphosphacarboranes
Author(s) -
McLellan Ross,
Bailo Marta,
Ellis David,
Rosair Georgina M.,
Welch Alan J.
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201300157
Subject(s) - deprotonation , heteroatom , chemistry , ligand (biochemistry) , stereochemistry , metal , carbon fibers , medicinal chemistry , molecule , crystallography , ring (chemistry) , organic chemistry , materials science , ion , biochemistry , receptor , composite number , composite material
Two new metallaphosphacarboranes have been synthesised from [7, 8‐ nido ‐CPB 9 H 11 ] – by deprotonation followed by treatment with a metal fragment. Starting with [HNMe 3 ][7, 8‐ nido ‐CPB 9 H 11 ] deprotonation and reaction with a source of {(indenyl)Co} 2+ affords the η‐bonded cobaltaphosphacarborane 3‐(η‐C 9 H 7 )‐3,1,2‐ closo ‐CoCPB 9 H 10 ( 1 ) the first “half‐sandwich“ 3,1,2‐metallaphosphacarborane. The indenyl ligand conformation in 1 ( cisoid between the indenyl bridgehead carbon atoms and cage heteroatoms, with the cage carbon atom lying below the indenyl C–C bond) reveals that the structural trans effect in a phosphacarborane ligand is weakest for carbon and therefore varies in the order B > P > C. Starting with [HNC 5 H 11 ][7, 8‐ nido ‐CPB 9 H 11 ] deprotonation and reaction with half an equivalent of [Ru( p ‐cymene)Cl 2 ] 2 affords the σ‐bonded ruthenaphosphacarborane 8‐{Ru( p ‐cymene)Cl(C 5 H 11 N)}‐7, 8‐ nido ‐CPB 9 H 11 ( 2 ), the first example of a molecule with a phosphacarborane σ‐bonded to a metal to be crystallographically characterised.