About this Chemistry article

A Terminal Hydride of Hafnium Supported by a Triamidoamine Ligand by Sebastian Schrader; Priyabrata Ghana; Alexander Hoffmann; Thomas P. Spaniol; Jun Okuda is a Chemistry article available to read on EtoBox.

A mononuclear hafnium hydride supported by an arylsubstituted triamidoamine ligand [HfH(thf)(Xy-N 3 N)] (Xy-N 3 N = {(3,5-Me 2 C 6 H 3 )NCH 2 CH 2 } 3 N 3-) was synthesized by either hydrogenolysis of the hydrocarbyl complex [Hf(R)(thf)(Xy-N 3 N)] (R = Me, CH 2 SiMe 3 , η 3 -C 3 H 5 , CH 2 Ph) in tetrahydrofuran (THF) or, more conveniently, by salt metathesis of the chloro precursor [HfCl(thf)(Xy-N 3 N)] with NaBEt 3 H in methylcyclohexane. The structure of a terminal hydride with a distorted capped trigonal bipyramidal geometry was characterized by single crystal X-ray diffraction (d(Hf-H): 1.83(3) Å) and by 1 H NMR spectroscopy. The unusually low field shifted 1 H chemical shift for the hydride ligand was detected at δ 18.28 ppm. Dehydrogenative thermolysis of the hydride complex at 25 °C in benzene or toluene resulted in deprotonation of the α-hydrogen of one of the three XyNCH 2 CH 2 groups in the ligand by the hydride, followed by the combination of this deprotonated anionic complex with cationic complex [Hf(Xy-N 3 N)] + to give an unsymmetric dinuclear complex bridged by μ-H, μ-NXy, and μ,κN,κC-XyNCHCH 2 groups. This decomposition product was characterized by single crystal X

Author

Sebastian Schrader; Priyabrata Ghana; Alexander Hoffmann; Thomas P. Spaniol; Jun Okuda

Publisher

American Chemical Society (ACS)

Published

2023

Language

EN

Field

Chemistry (Physical Sciences)