Isolation of Au-, Co-η1 PCO and Cu-η2 PCO complexes, conversion of an Ir-η1 PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion

Chemical Science
Liu Leo LiuHansjörg Grützmacher

Abstract

Sodium phosphaethynolate reacts with [MCl(PDI)] (M = Co, Ir; PDI = pyridinediimine) to give metallaphosphaketenes, which in the case of iridium rearranges into a dimetalladiphosphene, via CO migration from phosphorus to the metal. Two different bonding modes of the PCO anion to CAAC-coinage metal complexes [CAAC: cyclic (alkyl)(amino)(carbene)] are reported, one featuring a strong Au-P bond and the other an η2 coordination to copper. The gold complex appears to be mostly unreactive whereas the copper complex readily reacts with various organic substrates. A completely free PCO anion was structurally characterized as the [Cu(La)2]+ (OCP)- salt. It results from the simple displacement of the PCO unit of the cationic (CAAC)Cu(PCO) complex by a second equivalent of CAAC.

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Methods Mentioned

BETA
NMR
X-ray

Software Mentioned

Bruker SAINT +
SHELXS

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