Two-coordinate d9 complexes. synthesis and oxidation of NHC nickel(I) amides

Carl A Laskowski; Gregory L Hillhouse

doi:10.1021/ja805804s

Two-coordinate d9 complexes. synthesis and oxidation of NHC nickel(I) amides

J Am Chem Soc. 2008 Oct 22;130(42):13846-7. doi: 10.1021/ja805804s. Epub 2008 Sep 26.

Authors

Carl A Laskowski¹, Gregory L Hillhouse

Affiliation

¹ Gordon Center for Integrative Science, Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, USA.

PMID: 18817391
DOI: 10.1021/ja805804s

Abstract

Reaction of the d9-d9 Ni(I) monochloride dimer, [(IPr)Ni(mu-Cl)]2 (1), with NaN(SiMe3)2 and LiNHAr (Ar = 2,6-diisopropylphenyl) gives the novel monomeric, 2-coordinate Ni(I) complexes (IPr)Ni{N(SiMe3)2} (2) and (IPr)Ni(NHAr) (3). Reaction of 2 with Cp2Fe+ results in its 1-e- oxidation followed by beta-Me elimination to give a base-stabilized iminosilane complex [(IPr)Ni(CH3){kappa1-N(SiMe3)=SiMe2.Et2O}][BArF4] (6). Oxidation of 3 gives [(IPr)Ni(eta3-NHAr)(THF)][BArF4] (4), which upon loss of THF affords dimeric [(IPr)Ni(N,eta3:NHC6iPr2H3)]2[BArF4]2 (5).