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N‐Heterocyclic Carbene–Phosphinidene Complexes of the Coinage Metals
Author(s) -
Doddi Adinarayana,
Bockfeld Dirk,
Nasr Alexandre,
Bannenberg Thomas,
Jones Peter G.,
Tamm Matthias
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502208
Subject(s) - tetrahydrothiophene , chemistry , carbene , phosphinidene , medicinal chemistry , trifluoromethanesulfonate , cationic polymerization , adduct , metal halides , bimetallic strip , electrophile , metal , polymer chemistry , catalysis , organic chemistry
Coinage metal complexes of the N‐heterocyclic carbene–phosphinidene adduct IPr ⋅ PPh (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) were prepared by its reaction with CuCl, AgCl, and [(Me 2 S)AuCl], which afforded the monometallic complexes [(IPr ⋅ PPh)MCl] (M=Cu, Ag, Au). The reaction with two equivalents of the metal halides gave bimetallic [(IPr ⋅ PPh)(MCl) 2 ] (M=Cu, Au); the corresponding disilver complex could not be isolated. [(IPr ⋅ PPh)(CuOTf) 2 ] was prepared by reaction with copper(I) trifluoromethanesulfonate. Treatment of [(IPr ⋅ PPh)(MCl) 2 ] (M=Cu, Au) with Na(BAr F ) or AgSbF 6 afforded the tetranuclear complexes [(IPr ⋅ PPh) 2 M 4 Cl 2 ]X 2 (X=BAr F or SbF 6 ), which contain unusual eight‐membered M 4 Cl 2 P 2 rings with short cuprophilic or aurophilic contacts along the chlorine‐bridged M⋅⋅⋅M axes. Complete chloride abstraction from [(IPr ⋅ PPh)(AuCl) 2 ] was achieved with two equivalents of AgSbF 6 in the presence of tetrahydrothiophene (THT) to form [(IPr ⋅ PPh){Au(THT)} 2 ][SbF 6 ] 2 . The cationic tetra‐ and dinuclear complexes were used as catalysts for enyne cyclization and carbene transfer reactions.