Clusters [M<sub><i>a</i></sub>(GaCp*)<sub><i>b</i></sub>(CNR)<sub><i>c</i></sub>] (M =
Ni, Pd, Pt): Synthesis, Structure, and Ga/Zn Exchange Reactions
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Abstract
Reactions
of homoleptic isonitrile ligated complexes or clusters of d<sup>10</sup>-metals with the potent
carbenoid donor ligand GaCp* are presented (Cp* = pentamethylcyclopentadienyl).
Treatment of [Ni<sub>4</sub>(CN<i>t</i>-Bu)<sub>7</sub>], [{M(CNR)<sub>2</sub>}<sub>3</sub>] (M = Pd, Pt) and [Pd(CNR)<sub>2</sub>Me<sub>2</sub>] (R = <i>t</i>-Bu, Ph) with suitable
amounts of GaCp* lead to the formation of the heteroleptic, tri- and
tetranuclear clusters [Ni<sub>4</sub>(CN<i>t</i>-Bu)<sub>7</sub>(GaCp*)<sub>3</sub>] (<b>1</b>), [{M(CN<i>t</i>-Bu)}<sub>3</sub>(GaCp*)<sub>4</sub>] (M = Pd: <b>2a</b>, Pt: <b>2b</b>), and [{Pd(CNR)}<sub>4</sub>(GaCp*)<sub>4</sub>] (R = <i>t</i>-Bu: <b>3a</b>, Ph: <b>3b</b>). The reactions
involve isonitrile substitution reactions, GaCp* addition reactions,
and cluster formation reactions. The new compounds were investigated
for their ability to undergo Ga/Zn exchange reactions when treated
with ZnMe<sub>2</sub>. The novel tetranuclear Zn-rich clusters [Ni<sub>4</sub>GaZn<sub>7</sub>(Cp*)<sub>2</sub>Me<sub>7</sub>(CN<i>t</i>-Bu)<sub>6</sub>] (<b>4</b>) and [{Pd(CNR)}<sub>4</sub>(ZnCp*)<sub>4</sub>(ZnMe)<sub>4</sub>] (R = <i>t</i>-Bu: <b>5a</b>, Ph: <b>5b</b>) were obtained and isolated. The electronic
situation and geometrical arrangement of atoms of all compounds will
be presented and discussed. All new compounds are characterized by
solution <sup>1</sup>H, <sup>13</sup>C NMR and IR spectroscopy, elemental
analysis (EA), liquid injection field desorption ionization mass spectrometry
(LIFDI-MS) as well as single crystal X-ray crystallography
