%0 Journal Article
%A Lipschutz, Michael
I.
%A Tilley, T. Don
%D 2015
%T Useful Method for the Preparation of Low-Coordinate
Nickel(I) Complexes via Transformations of the Ni(I) Bis(amido) Complex
K{Ni[N(SiMe3)(2,6‑iPr2‑C6H3)]2}
%U https://acs.figshare.com/articles/journal_contribution/Useful_Method_for_the_Preparation_of_Low_Coordinate_Nickel_I_Complexes_via_Transformations_of_the_Ni_I_Bis_amido_Complex_K_Ni_N_SiMe_sub_3_sub_2_6_sup_i_i_i_sup_Pr_sub_2_sub_C_sub_6_sub_H_sub_3_sub_sub_2_sub_/2041749
%R 10.1021/om500849u.s001
%2 https://acs.figshare.com/ndownloader/files/3613065
%K ligand
%K phenoxide acts
%K acceptor
%K Ni
%K HN
%K HO
%K NHC
%K complex
%K DPPE
%X A convenient
method of preparing two- and three-coordinate Ni(I)
complexes of the form L–NiI–X (L = PtBu3, PiPr3, DPPE, NHC; X = −N(SiMe3)(2,6-iPr-C6H3), −O(2,6-tBu2-4-Me-C6H2)) is reported. Protonation of the easily prepared anionic Ni(I)
bis(amido) complex K{Ni[N(SiMe3)(2,6-iPr-C6H3)]2} in the
presence of an appropriate L-type ligand results in loss of HN(SiMe3)(2,6-iPr-C6H3) and trapping of the resulting neutral Ni(I)-amido fragment
to yield neutral, paramagnetic, two- and three-coordinate Ni(I) complexes.
Protonation of these neutral amido complexes by the bulky phenol HO(2,6-tBu2-4-Me-C6H2) results in loss of the second amido moiety and trapping by the
resulting phenoxide to yield Ni(I)-O(2,6-tBu2-4-Me-C6H2) complexes. The hapticity
of the phenoxide ligand is influenced by the π-accepting ability
of the L-type ligand. Where L = PtBu3, a poor π-acceptor, the phenoxide acts as a π-acceptor
and adopts a η5-bonding mode through dearomatization
of the phenyl ring. When L = NHC, a competent π-acceptor, the
phenoxide acts as a π-donor, adopting a η1-bonding
mode through the O atom. The modular nature of this synthetic strategy
allows variation of both the L- and X-type ligands of the complex
in a stepwise fashion and should be extendable to a wide variety of
ligand types for new Ni(I) complexes.
%I ACS Publications