New neutral organometallic palladium(II) complexes, [PdPhI(PNMe2)] (1), [PdPhI(PC=NMe)] (2), [PdPhI(PC=NEt)] (3), and [PdMeCl(PNMe2)] (4), {PNMe2 means N,N-dimethyl2-(diphenylphosphanyl)aniline; PC=NMe means N-[2-(diphenylphosphanyl) benzylidene]-N-methylamine; PC=NEt means N-[2- (diphenylphosphanyl)benzylidene]-N-ethylamine} have been synthesized by oxidative addition of PhI to [Pd(dba)(2)] in the presence of the (PN)-N-boolean AND ligand (1-3), or by substitution reaction on [PdMeCl(COD)] with PNMe2 (4). Cationic sigma-organometallic species [PdR(PPh3)((PN)-N-boolean AND)](+) are obtained upon treating complexes of the type [PdRX((PN)-N-boolean AND)] with PPh3 and AgCF3SO3 and consist predominantly of the trans-P,P isomer in CDC13 solution, as shown by NMR spectroscopic studies. The cationic eta(3)-allyl complex [Pd(eta(3)-all)(PNMe2)]PF6 has also been prepared and characterized, both in solution and in the solid state. Compounds [PdPhI(PNMe2)] (P2(1)/n), [PdPhI(PC=NMe)] (P (1) over bar), [PdPhI(PC=NEt)] (P (1) over bar), and [Pd(eta(3)-all) (PNMe2)]PF6 (P (1) over bar) have been authenticated by X-ray analysis
New organometallic palladium(II) complexes containing PN ligands. Synthesis, characterization and X-ray structure.
CROCIANI, LAURA;BANDOLI, GIULIANO;DOLMELLA, ALESSANDRO;BASATO, MARINO;CORAIN, BENEDETTO
1998
Abstract
New neutral organometallic palladium(II) complexes, [PdPhI(PNMe2)] (1), [PdPhI(PC=NMe)] (2), [PdPhI(PC=NEt)] (3), and [PdMeCl(PNMe2)] (4), {PNMe2 means N,N-dimethyl2-(diphenylphosphanyl)aniline; PC=NMe means N-[2-(diphenylphosphanyl) benzylidene]-N-methylamine; PC=NEt means N-[2- (diphenylphosphanyl)benzylidene]-N-ethylamine} have been synthesized by oxidative addition of PhI to [Pd(dba)(2)] in the presence of the (PN)-N-boolean AND ligand (1-3), or by substitution reaction on [PdMeCl(COD)] with PNMe2 (4). Cationic sigma-organometallic species [PdR(PPh3)((PN)-N-boolean AND)](+) are obtained upon treating complexes of the type [PdRX((PN)-N-boolean AND)] with PPh3 and AgCF3SO3 and consist predominantly of the trans-P,P isomer in CDC13 solution, as shown by NMR spectroscopic studies. The cationic eta(3)-allyl complex [Pd(eta(3)-all)(PNMe2)]PF6 has also been prepared and characterized, both in solution and in the solid state. Compounds [PdPhI(PNMe2)] (P2(1)/n), [PdPhI(PC=NMe)] (P (1) over bar), [PdPhI(PC=NEt)] (P (1) over bar), and [Pd(eta(3)-all) (PNMe2)]PF6 (P (1) over bar) have been authenticated by X-ray analysis
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