Mechanisms of Thermal Decomposition oftrans- andcis-Dialkylbis(tertiary phosphine)palladium(II). Reductive Elimination andtranstocisIsomerization
作者： Fumiyuki Ozawa , Takashi Ito , Yoshiyuki Nakamura , Akio Yamamoto
DOI: 10.1246/BCSJ.54.1868
关键词:
摘要: Series of trans- and cis-dialkylpalladium(II) complexes having tertiary phosphine ligands (L) various basicities bulkiness have been prepared their thermolysis isomerization mechanisms in solution studied. Examination the cause selective formation cis-dialkyl isomers by using alkyllithium revealed a new type trans to cis promoted alkyllithium. A process involving trialkyl-palladate intermediate is proposed as mechanism for isomerization. Evidence support has obtained experiments LiCD3. Thermolysis cis-PdR2L2 demonstrated proceed through unimolecular initiated rate-determining dissociation L produce three-coordinate “cis-PdR2L” which reductively eliminates R groups. Addition free ligand system containing cis-PdMe2L2 effectively blocks reductive elimination pathway thus forcing complex be thermolyzed route involving...
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