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Synthesis, Structure, and Reactivity of a Mononuclear η 2 ‐(Ge–H)palladium(0) Complex Bearing a PGeP‐Pincer‐Type Germyl Ligand: Reactivity Differences between Silicon and Germanium
Author(s) -
Takaya Jun,
Iwasawa Nobuharu
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201801257
Subject(s) - chemistry , palladium , reactivity (psychology) , ligand (biochemistry) , germanium , pincer movement , silylation , organometallic chemistry , dimer , crystallography , silicon , stereochemistry , thermal decomposition , metal , transition metal , crystal structure , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology
Reactivity differences between silicon and germanium as supporting ligands in PEP‐pincer type palladium complexes (E = Si, Ge) were clarified by experimental and theoretical studies. An η 2 ‐(Ge–H)palladium(0) complex, which was synthesized and structurally characterized for the first time, exhibited higher reactivity for hydrometallation of ethylene than the silyl‐analogue. The resulting PGeP‐ethylpalladium(II) complex was more stable than the silyl‐analogue, which allowed its isolation and structural analysis by X‐ray crystallography. Formation of a Ge‐bridged Pd dimer complex by thermal decomposition of the η 2 ‐(Ge–H)palladium(0) complex was also demonstrated. Experimental and theoretical studies clarified that the germanium ligand stabilizes the Pd II state with the Pd–E bond and destabilizes the η 2 ‐(E–H)Pd 0 state compared to the case of the silicon ligand. This study provided useful insights for rational design of transition metal complexes bearing a heavier group 14 element as a supporting ligand in organometallic chemistry.