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POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities

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Abstract

A series of iminophosphinite POCN pincer Ni(II) complexes, (POCN)NiMe and (POCN)NiLn(BX4) (L = CH3CN, n = 0, 1; X = F, Ph, C6F5), have been developed and subjected to catalytic hydrosilylation of alkenes, aldehydes and ketones and hydroboration of carbonyl compounds. The stoichiometric reactivity of (POCN)NiMe and (POCN)Ni(BF4) with PhSiH3 and HBPin suggests that catalytic reactions proceed via the hydride intermediate (POCN)NiH. With regard to reactions with HBPin, efficient and mild hydroboration of a variety of carbonyl compounds, including highly chemoselective hydroboration of benzaldehyde in the presence of other common potent reductive functional groups, such as alkenes, alkynes, esters, amides, nitriles, nitro compounds and even ketones, and the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary and secondary amides to borylated amines were demonstrated for (POCN)NiMe.

Graphical abstract: POCN Ni(ii) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities

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Publication details

The article was received on 08 Dec 2018, accepted on 27 Dec 2018 and first published on 03 Jan 2019


Article type: Paper
DOI: 10.1039/C8DT04854A
Citation: Dalton Trans., 2019, Advance Article
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    POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities

    K. A. Gudun, M. Segizbayev, A. Adamov, P. N. Plessow, K. A. Lyssenko, M. P. Balanay and A. Y. Khalimon, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C8DT04854A

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