Literature DB >> 20043681

Mechanism of heterolysis of H2 by an unsaturated d8 nickel center: via tetravalent nickel?

Tao He1, Nikolay P Tsvetkov, José G Andino, Xinfeng Gao, Benjamin C Fullmer, Kenneth G Caulton.   

Abstract

Collision of H(2) with the unusual nickel complex, (PNP)Ni(+), where PNP = ((t)Bu(2)PCH(2)SiMe(2))(2)N, forms a rare dihydrogen complex of the d(8) configuration which then rearranges to heterolytically cleave the H-H bond. Experimental studies support a short H/H distance in the coordinated diatomic, and DFT calculations show that the transition state for heterolysis, in spite of the fact that this involves an amide nitrogen located trans to the H(2), has the H/H bond fully split, and has all the geometric features of Ni(IV), but this is a local maximum, not a minimum.

Entities:  

Year:  2010        PMID: 20043681     DOI: 10.1021/ja908674x

Source DB:  PubMed          Journal:  J Am Chem Soc        ISSN: 0002-7863            Impact factor:   15.419


  5 in total

Review 1.  Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides.

Authors:  David Schilter; James M Camara; Mioy T Huynh; Sharon Hammes-Schiffer; Thomas B Rauchfuss
Journal:  Chem Rev       Date:  2016-06-29       Impact factor: 60.622

2.  Homoleptic nickel(II) complexes of redox-tunable pincer-type ligands.

Authors:  Jeewantha S Hewage; Sarath Wanniarachchi; Tyler J Morin; Brendan J Liddle; Megan Banaszynski; Sergey V Lindeman; Brian Bennett; James R Gardinier
Journal:  Inorg Chem       Date:  2014-09-15       Impact factor: 5.165

3.  Active-site models for the nickel-iron hydrogenases: effects of ligands on reactivity and catalytic properties.

Authors:  Maria E Carroll; Bryan E Barton; Danielle L Gray; Amanda E Mack; Thomas B Rauchfuss
Journal:  Inorg Chem       Date:  2011-08-25       Impact factor: 5.165

4.  Heterolytic Cleavage of Dihydrogen by an Iron(II) PNP Pincer Complex via Metal-Ligand Cooperation.

Authors:  Bernhard Bichler; Christian Holzhacker; Berthold Stöger; Michael Puchberger; Luis F Veiros; Karl Kirchner
Journal:  Organometallics       Date:  2013-07-26       Impact factor: 3.876

5.  Ambiphilic boryl groups in a neutral Ni(ii) complex: a new activation mode of H2.

Authors:  Pablo Ríos; Javier Borge; Francisco Fernández de Córdova; Giuseppe Sciortino; Agustí Lledós; Amor Rodríguez
Journal:  Chem Sci       Date:  2020-12-22       Impact factor: 9.825

  5 in total

北京卡尤迪生物科技股份有限公司 © 2022-2023.