The transmetalation reaction of picolyl-supported tridentate
nacnac
germylene monochloride [2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)]GeCl (1) (py = pyridine) with SnCl2 results in an analogous
stannylene chloride (2). The three-coordinated stannylenium
cation [{2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)}Sn]+ with
SnCl3
– as a counteranion (3) has been generated through the abstraction of chloride ligand from 2 using an additional equivalent of SnCl2. Instead
of forming a donor–acceptor complex, 2 undergoes
a facile redox transmetalation reaction with Ni(COD)2 (COD
= cyclooctadiene) and CuCl to afford analogous nickel and copper complexes
[2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)]MCl [M = Ni (4) and
Cu (5)]. The reactions of 4 with potassium
tri-sec-butylborohydride (commonly known as K-selectride)
and AgSbF6 provide access to monomeric Ni(II) hydride,
[2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)]NiH (6) and a Ni(II)
cation, [{2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)}Ni][SbF6] (7), respectively. 6 was found to be
an effective catalyst for the hydroboration of amides.
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