Abstract
We report on the synthesis of novel coinage metal NHC (N-heterocyclic carbene) compounds of the germanium-rich metalloid clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr)3 and RI = Si(TMS)3. NHCDippCu{η3-Ge9R3} with R = Si(iPr)3 (1) represents a less bulky silyl group-substituted derivative of the known analogous compounds with R = Si(iBu)3 or Si(TMS)3. The coordination of the [NHCDippCu]+ moiety to the cluster unit occurs via one triangular face of the tri-capped trigonal prismatic [Ge9] cluster. Furthermore, a series of novel Zintl cluster coinage metal NHC compounds of the type (NHCM)2{η3-Ge9RI2} (RI = Si(TMS)3 M = Cu, Ag and Au; NHC = NHCDipp or NHCMes) is presented. These novel compounds represent a new class of neutral dinuclear Zintl cluster coinage metal NHC compounds, which are obtained either by the stepwise reaction of a suspension of K12Ge17 with Si(TMS)3Cl and the coinage metal carbene complexes NHCMCl (M = Cu, Ag, Au), or via a homogenous reaction using the preformed bis-silylated cluster K2[Ge9(Si(TMS)3)2] and the corresponding NHCMCl (M = Cu, Ag, Au) complex. The molecular structures of NHCDippCu{η3-Ge9(Si(iPr)3)3} (1) and (NHCDippCu)2{η3-Ge9(Si(TMS)3)2} (2) were determined by single crystal X-ray diffraction methods. In 2, the coordination of the [NHCDippCu]+ moieties to the cluster unit takes place via both open triangular faces of the [Ge9] entity. Furthermore, all compounds were characterized by means of NMR spectroscopy (1H, 13C, 29Si) and ESI-MS.
Highlights
Polyatomic Zintl clusters [E9 ]4− or [E4 ]4− (E: tetrel element) can be extracted from the neat solids of their alkali metal salts with the compositions A4 E9 and A12 E17 (A = alkali metal, E = Si-Pb) and are accessible for further reactions
Compounds of the type (NHCM)2 {η3 -Ge9 RI 2 } (RI = Si(TMS)3 M = Cu, Ag and Au; N-heterocyclic carbene ligands (NHCs) = NHCDipp or NHCMes ) is presented. These novel compounds represent a new class of neutral dinuclear Zintl cluster coinage metal NHC compounds, which are obtained either by the stepwise reaction of a suspension of K12 Ge17 with Si(TMS)3 Cl and the coinage metal carbene complexes NHCMCl (M = Cu, Ag, Au), or via a homogenous reaction using the preformed bis-silylated cluster K2 [Ge9 (Si(TMS)3 )2 ]
In continuation of our work, we examined the reactivity of coinage metal carbene compounds towards silylated Zintl clusters and studied the impact of a tris-silylated cluster ligand, bearing the sterically less bulky silyl group [Si(i Pr)3 ]+ on the structure of the resulting Cu-NHC complex
Summary
Polyatomic Zintl clusters [E9 ]4− or [E4 ]4− (E: tetrel element) can be extracted from the neat solids of their alkali metal salts with the compositions A4 E9 and A12 E17 (A = alkali metal, E = Si-Pb) and are accessible for further reactions. A large number of transition metal compounds containing Zintl cluster ligands have been reported. Precursors, especially of the late transition metals (groups 10, 11 and 12), have successfully been treated with these anionic Zintl clusters [2,3]. The addition of early transition metal fragments to Zintl clusters has been recently achieved [4]. Reactions of Zintl clusters with coinage metal precursor complexes and Zn organyls revealed that the addition of a metal atom to the bare clusters can initiate cluster growth under
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