Carbene insertion into a P–H bond: parent phosphinidene–carbene adducts from PH3 and bis(phosphinidene)mercury complexes. Issue 14 (30th June 2015)

• Record Type: Journal Article
• Authors: Bispinghoff, Mark; Tondreau, Aaron M.; Grützmacher, Hansjörg; Faradji, Charly A.; Pringle, Paul G.
• Is Part Of: Dalton transactions. Volume 45:Issue 14(2016)
• Page Start: 5999
• Page End: 6003
• Publication Date: 2015-06-30
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt01741f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The insertion of an N-heterocyclic carbene into a P–H bond is the first step in a new synthesis of parent phosphinidene–carbene adducts from PH3 . These adducts are used to generate bis(phosphinidene)mercury(ii ) complexes. Abstract : PH3 reacts with the in situ generated N-heterocyclic carbene DippNHC* (DippNHC* = 1, 3-bis(2, 6-diisopropylphenyl)imidazolin-2-ylidene) to give the phosphanyl–imidazolidine [ Dipp NHC*-H]-[PH2 ]. Upon treatment with an ortho -quinone, [ Dipp NHC*-H]-[PH2 ] is dehydrogenated to give the parent phosphinidene–carbene adduct Dipp NHC*PH. Alternative routes to [ Dipp NHC*-H]-[PH2 ] and Dipp NHC*PH employ NaPH2 and (TMS)3 P7 (TMS = trimethylsilyl), respectively, as phosphorus sources. The adduct Dipp NHC*PH and the related adduct Dipp NHCPH ( Dipp NHC = bis(2, 6-diisopropylphenyl)imidazol-2-ylidene) possessing an unsaturated NHC backbone both react with HgCl2 to give the bis(carbene–phosphinidenyl) complexes [( Dipp NHC*P)2 Hg] and [( Dipp NHCP)2 Hg].