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Synthetic investigations of low-coordinate (N-phosphino-amidinate) nickel chemistry: agostic alkyl complexes and benzene insertion into Ni–H

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Abstract

Treatment of (PN)NiX (X = NHdipp or OtBu; PN = N-phosphinoamidinate ligand) with Me2PhSiH in benzene solvent afforded the crystallographically characterized, antifacial-coordinated, dinuclear species 1, the formation of which corresponds to the hitherto unknown net Ni–H addition of two equivalents of the putative (PN)NiH intermediate across C[double bond, length as m-dash]C units within a single benzene molecule. Computational analysis supports the view of 1 as being comprised of two cationic (PN)NiII fragments ligated by a substituted butadiene dianion μ2–η33-C6H82− bridging group. Also described is the formation and characterization of three-coordinate (PN)Ni(alkyl) complexes stabilized by β-agostic (alkyl = Et, 2; n-Bu, 3; n-hexyl, 4) or γ-agostic (alkyl = neopentyl, 5) interactions, and our efforts to employ 2 and 3 as synthons for the generation of (PN)NiH via β-hydride elimination. Notably, compound 5 represents both the first crystallographically characterized three-coordinate Ni-alkyl complex featuring a heterobidentate ligation, and the first neutral γ-agostic NiII-alkyl complex.

Graphical abstract: Synthetic investigations of low-coordinate (N-phosphino-amidinate) nickel chemistry: agostic alkyl complexes and benzene insertion into Ni–H

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Supplementary files

Article information


Submitted
13 Feb 2020
Accepted
19 Mar 2020
First published
19 Mar 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Synthetic investigations of low-coordinate (N-phosphino-amidinate) nickel chemistry: agostic alkyl complexes and benzene insertion into Ni–H

C. M. Macaulay, M. Samolia, M. J. Ferguson, O. L. Sydora, D. H. Ess, M. Stradiotto and L. Turculet, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT00527D

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