Premium
Synthesis, Characterization, and Interconversion of β‐Diketiminato Nickel N x H y Complexes
Author(s) -
Köthe Claudia,
Braun Beatrice,
Herwig Christian,
Limberg Christian
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402812
Subject(s) - chemistry , deprotonation , nickel , protonation , hydrazine (antidepressant) , medicinal chemistry , bond cleavage , stereochemistry , crystallography , catalysis , organic chemistry , ion , chromatography
The β‐diketiminato nickel(II) hydrazido(–1) complex [L t Bu Ni(η 2 ‐N 2 H 3 )], ( IV ) was investigated with respect to its deprotonation/protonation behavior. Deprotonation with KO t Bu led to [L t Bu Ni(μ,η 2 :η 2 ‐N 2 H 2 )K(solv)] ( 1 ), and this process was proven to be reversible. Spectroscopic and DFT studies revealed an electronic structure intermediate between nickel(II) hydrazido(–2) and nickel(0) diazene. On the other hand, protonation of IV with [LutH]OTf reversibly generated the hydrazine complex [L t Bu Ni(η 2 ‐N 2 H 4 )]OTf ( 2 ). Warming a solution of IV led to N–N bond cleavage yielding the nickel(I) ammine complex [L t Bu Ni(NH 3 )], ( 3 ). Hence, L t Bu Ni moieties were shown to effectively activate N x H y species for diverse conversions.