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Benzoimidazole‐Pyridylamido Zirconium and Hafnium Alkyl Complexes as Homogeneous Catalysts for Tandem Carbon Dioxide Hydrosilylation to Methane
Author(s) -
Luconi Lapo,
Rossin Andrea,
Tuci Giulia,
Gafurov Zufar,
Lyubov Dmitrii M.,
Trifonov Alexander A.,
Cicchi Stefano,
Ba Housseinou,
PhamHuu Cuong,
Yakhvarov Dmitry,
Giambastiani Giuliano
Publication year - 2019
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201800077
Subject(s) - chemistry , hydrosilylation , ligand (biochemistry) , denticity , alkyl , medicinal chemistry , coordination sphere , catalysis , lewis acids and bases , pyridine , homogeneous catalysis , stereochemistry , metal , organic chemistry , biochemistry , receptor
Neutral Zr IV and Hf IV alkyl/amido complexes stabilized by a tridentate N ligand that contains a “rolling” heterodentate benzoimidazole fragment have been prepared and characterized. The ultimate nature of the ligand denticity, the electronic properties of the ligand binding pocket and the metal coordination environment are controlled by the protection/deprotection of the benzoimidazole NH group. The metal precursor used [M IV (Bn) 4 or M IV (NMe 2 ) 4 ] also has an influence on the final coordination sphere of the complex; indeed, a permanent central pyridine dearomatization occurs in the presence of dimethylamido ancillary groups. DFT calculations on the real system have been used to elucidate the mechanism. Selected alkyl species from this series have been scrutinized for the tandem hydrosilylation of CO 2 to CH 4 in combination with the strong Lewis acid B(C 6 F 5 ) 3 using a variety of hydrosilanes. A positive effect of the hardness modification of the ligand donor atom set is observed in the catalytic outcomes. Indeed, κ 3 { N − , N , N − }Zr IV (Bn) 2 catalyzes the process to methane selectively with a turnover frequency as high as 272 h −1 (at 96 % substrate conversion) almost twice as much as that claimed for the benchmark κ 3 { O − , O , O − }Zr IV (Bn) 2 complex under similar experimental conditions.