Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i), ligand substitution, and unusual P-4 fragmentation
OPEN ACCESS
Loading...
Author / Producer
Date
2021
Publication Type
Journal Article
ETH Bibliography
yes
Citations
Altmetric
OPEN ACCESS
Data
Rights / License
Abstract
Oxidative addition of the P-P single bond of an ortho-carborane-derived 1,2-diphosphetane (1,2-C-2(PMes)(2)B10H10) (Mes = 2,4,6-Me3C6H2) to cobalt(-i) and nickel(0) sources affords the first heteroleptic complexes of a carborane-bridged bis(phosphanido) ligand. The complexes also incorporate labile ligands suitable for further functionalisation. Thus, the cobalt(i) complex [K([18]crown-6)][Co{1,2-(PMes)(2)C2B10H10}(cod)] (cod = 1,5-cyclooctadiene) bearing a labile cyclooctadiene ligand undergoes facile ligand exchange reactions with isonitriles and tert-butyl phosphaalkyne with retention of the bis(phosphanido) ligand. However, in the reaction with one equivalent of P-4, the electron-rich bis(phosphanido) moiety abstracts a single phosphorus atom with formation of a new P-3 chain, while the remaining three P atoms derived from P-4 form an eta(3)-coordinating cyclo-P-3 ligand. In contrast, when the same reaction is performed with two equivalents of the cobalt(i) complex, a dinuclear product is formed which features an unusual P-4 chain in its molecular structure.
Permanent link
Publication status
published
External links
Editor
Book title
Journal / series
Volume
12 (33)
Pages / Article No.
11225 - 11235
Publisher
Royal Society of Chemistry