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Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon
Ist Teil von
Angewandte Chemie (International ed.), 2014-08, Vol.53 (34), p.9068-9071
Auflage
International ed. in English
Ort / Verlag
Weinheim: WILEY-VCH Verlag
Erscheinungsjahr
2014
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
Readily accessible nitrilium triflates are convenient imine building blocks for the expedient synthesis of a novel class of 1,3‐P,N ligands as demonstrated for the reaction with primary phosphanes. This procedure allows variation of all substituents. X‐ray crystal structures are reported for nitrilium ions, phosphaamidines, and three phosphaamidinate complexes. The lithium phosphaamidinate is N coordinated and its reaction with [AuCl(tht)] (tht=tetrahydrothiophene) gives a unique P‐bridged gold trimer, while a P,N‐bidentate complex results from [{RhCl(cod)}2]. The nitrilium ion methodology allows extension of the 1,3‐P,N motive to bis(imino)phosphanes, which are the neutral phosphorus analogues of the valuable β‐diketiminate ligand.
P bridges: Readily accessible nitrilium triflates are convenient imine building blocks for the expedient synthesis of phosphaamidines as demonstrated for the reaction with primary phosphanes (see Scheme). Lithiation of these species provides access to phosphaamidinates, of which the coordination to [AuCl(tht)] gives a unique P‐bridged gold trimer, while [{RhCl(cod)}2] gives bidentate coordination. cod=1,5‐cyclooctadiene, tht=tetrahydrothiophene.