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4704292 
Journal Article 
Synthesis and structures of eta(1)-allenyl and/or -propargyl Pd(II) complexes and their reactivity toward trimethylsilyl pseudohalides, organic thiols, and N-heterocyclic carbene ligands 
Kim, YJoo; Kim, HK; Lee, JH; Zheng, ZNu; Lee, SW 
2013 
1 
Inorganica Chimica Acta
ISSN: 0020-1693
EISSN: 1873-3255 
398 
54-63 
WOS:000316742500007 
Facile oxidative additions of various propargyl halides to [Pd(CH2=CHPh)(PR3)(2)], which could be generated in situ from trans-[PdEt2(PR3)(2)] (PR3=PMe3, PEt3, PMe2Ph) and styrene, gave the bis(phosphine) eta(1)-allenyl and/or eta(1)-propargyl Pd(II) complexes. The chloro ligand in the eta(1)-allenyl Pd(II) complex could be replaced by pseudohalides to produce the new corresponding pseudohalo complexes, trans[ XPd(CH=C=CH2)(PMe3)(2)], when treated with trimethylsilyl pseudohalides (Me3SiX: X = NCS, CN, N-3). The eta(1)-allenyl complex was also converted into the thiolato complexes when treated with various organic thiols. In addition, the phosphine ligand in the eta(1)-allenyl complex could be replaced by NHC (N-heterocyclic carbene) to produce eta(1)-allenyl or - propargyl Pd(II) complex possessing the NHC ligand, depending on the coordinated eta(1)-allenyl moiety. On the other hand, oxidative addition of phenyl propargyl sulfide to the [Pd(CH2@ CHPh)(PMe3)(2)] gave a phenyl thiolato eta(1)-allenyl Pd(II) complex, trans[( C6H5S) Pd(CH=C=CH2)(PMe3)(2)]. (C) 2012 Elsevier B.V. All rights reserved. 
Allenyl complexes; Propargyl complexes; Trimethylsilyl isothiocyanate; Trimethyl cyanide; Trimethylsilyl azide; Palladium