[Si(SiMe3)3]6Ge18M (M = Cu, Ag, Au): metalloid cluster compounds as unusual building blocks for a supramolecular chemistry

Schenk, Christian; Henke, Florian; Santiso‐Quiñones, Gustavo; Krossing, Ingo; Schnepf, Andreas

doi:10.1039/b717506j

Cited by 103 publications

(82 citation statements)

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“…The formation of 1 can be viewed in light of the previously suggested formation of the gold analogue of 3, that is, [(Ge 9 R 3 )Au I (Ge 9 R 3 )] − (4). 46 While 3 is made by reacting Ge 9 R 3 − with the salt-like Cu(I) compound with weakly coordinating anions, Cu(Al(OR) 4 ), 47 4 is made by a reaction with a salt with ligated Au(I), (PPh 3 )AuCl, just like the reaction with (PPh 3 ) 3 CuBr for the formation of 1. It has been speculated that the formation of 4 begins with a salt-metathesis reaction to form the neutral [(Ge 9 R 3 )Au−PPh 3 ], which then exchanges the neutral PPh 3 ligand with another anionic Ge 9 R 3 − to form [(Ge 9 R 3 )Au I (Ge 9 R 3 )] − , that is: 46…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Coordination of Tri-Substituted Nona–Germanium Clusters to Cu(I) and Pd(0)

Sevov

2015

Inorg. Chem.

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The recently developed approach for the rational functionalization of deltahedral nona-germanium clusters Ge9(4-) with three substituents to form Ge9R3(-) (R = Si(SiMe3)3) in large amounts has made the latter a convenient starting material for further reactivity studies. Reported here are the synthesis, structures, and solution studies of two compounds where Ge9R3(-) are used as ligands to transition metals, [(Ge9R3)Cu(I)(Ge9R3)Cu(I)PPh3] (1) and [(Ge9R3)Pd(0)(Ge9R3)](2-) (2). The former adds to the families of anionic [(Ge9R3)M(I)(Ge9R3)](-) (M(I) = Cu, Ag, and Au) as a neutral member and of the neutral [(Ge9R3)M(II)(Ge9R3)] (M(II) = Zn, Cd, and Hg), while the latter represents the first compound involving a metal from group 10.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Coordination of Tri-Substituted Nona–Germanium Clusters to Cu(I) and Pd(0)

Sevov

2015

Inorg. Chem.

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“…X compounds (X = À1: M = Cu, Ag, Au; [23,24] X = 0: M = Zn, Cd, Hg [25] ). We now present a second example of a metalloid maingroup cluster exclusively stabilized by transition-metal-based ligands, showing a unique arrangement of the tetrel atoms in the cluster core.…”

Section: àmentioning

confidence: 99%

[Ge₁₂{FeCp(CO)₂}₈{FeCp(CO)}₂]: A Ge₁₂ Core Resembles the Arrangement of the High‐Pressure Modification Germanium (II)

2013

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Metalloid cluster compounds [1] of the general formula M n R m (n > m; R = ligand such as Si(SiMe 3 ) 3 or N(SiMe 3 ) 2 ) are ideal model compounds for molecular entities in the gray area between molecules and the solid state. [2] This borderland is of particular interest especially for metals or semi-metals, as drastic changes in the physical properties take place during the reduction from salt-like oxidized compounds (e.g. oxides, halides: non-conducting) to the elemental bulk phase (metal: conducting; semi-metal: semiconducting).[3] As the dimensions of metalloid clusters are in the nanometer range, the synthesis of metalloid clusters also opens the possibility of obtaining structural information on small nanoparticles, an important prerequisite for structure-property relations in this expanding area. [4] In the case of germanium, several different synthetic routes have been introduced in recent years, leading to a number of metalloid clusters, which exhibit new and unusual structures as well as exceptional bonding properties. Hence, by a reductive elimination reaction [Ge 10 (SitBu 3 ) 6 I]+ is obtained, [5] whereas the metalloid clusters [Ge 5 {CH-(SiMe 3 ) 2 } 4 ][6] and [Ge 6 (C 6 H 3 Dipp 2 ) 2 ] (Dipp = 2,6-iPr 2 C 6 H 3 ) [7] have been synthesized by reductive coupling reactions. The most fruitful route to metalloid germanium clusters to date uses the disproportionation reaction of dissolved metastable Ge I halides, which thus allows the synthesis of clusters with eight [Ge 8 {N(SiMe 3 ) 2 } 6 ], [8] [Ge 8 {(OtBu) 2 C 6 H 3 } 6 ], [9] nine [Ge 9 {Si(SiMe 3 ) 3 } 3 ]À , [10] ten [Ge 10 Si{Si(SiMe 3 ) 3 } 4 -(SiMe 3 ) 2 Me] À , [11] [Ge 10 {Fe(CO) 4 } 8 {Na(thf) 3 } 6 ], [12] and up to fourteen [Ge 14 {E(SiMe 3 ) 3 } 5 {Li(thf) 2 } 3 ] (E = Si, Ge) [13,14] germanium atoms in the cluster core.Among metalloid main-group clusters in general [Ge 10 {Fe(CO) 4 } 8 {Na(thf) 3 } 6 ] is an exceptional example as it is the only metalloid cluster which is exclusively stabilized by transition-metal-based ligands. This shows that the influence of transition-metal ligands on metalloid clusters is nearly unexplored. Furthermore, such metalloid clusters stabilized with transition-metal-based ligands might open an access to new metastable binary materials.[15] However, transitionmetal reagents have already been used in the chemistry of germanium clusters; either as ligands in direct synthesis to gain fully substituted clusters, such as [Ge 6 {Cr(CO) 5 X compounds (X = À1: M = Cu, Ag, Au;[23, 24] X = 0: M = Zn, Cd, Hg [25] ). We now present a second example of a metalloid maingroup cluster exclusively stabilized by transition-metal-based ligands, showing a unique arrangement of the tetrel atoms in the cluster core. After work up of a reaction mixture of a metastable GeBr solution (CH 3 CN, THF, nBu 3 N (2:2:1); 0.28 m) with solid K[FeCp(CO) 2 ] (Cp = cyclopentadienyl) we obtained black crystals of the metalloid germanium cluster [Ge 12 {FeCp(CO) 2 } 8 {FeCp(CO)} 2 ] (1). The molecular structure of 1, as shown in Figure ...

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“…The resulting bis- and tris-silylated cluster species [Ge 9 R 2 ] 2− (R = Si(TMS) 3 ) [14] and [Ge 9 R 3 ] − (R: various silyl groups) [15,16,17,18,19,20] are, due to their lower charge, soluble in common solvents (acetonitrile, thf, toluene). Subsequent reactions of the tris-silylated cluster [Ge 9 R 3 ] − (R: Si(TMS) 3 ) with coinage metal complexes, in most cases coinage metal phosphine complexes, commonly yield coinage metal-bridged cluster dimers, under the loss of the original ligand sphere of the transition metal [19,21,22]. However, there are also a few reports in which the Cu-phosphine bond is retained [18,23].…”

Section: Introductionmentioning

confidence: 99%

N-Heterocyclic Carbene Coinage Metal Complexes of the Germanium-Rich Metalloid Clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr)3 and RI = Si(TMS)3

et al. 2017

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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.

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[Si(SiMe3)3]6Ge18M (M = Cu, Ag, Au): metalloid cluster compounds as unusual building blocks for a supramolecular chemistry

Cited by 103 publications

References 36 publications

Coordination of Tri-Substituted Nona–Germanium Clusters to Cu(I) and Pd(0)

Coordination of Tri-Substituted Nona–Germanium Clusters to Cu(I) and Pd(0)

[Ge₁₂{FeCp(CO)₂}₈{FeCp(CO)}₂]: A Ge₁₂ Core Resembles the Arrangement of the High‐Pressure Modification Germanium (II)

N-Heterocyclic Carbene Coinage Metal Complexes of the Germanium-Rich Metalloid Clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr)3 and RI = Si(TMS)3

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[Si(SiMe3)3]6Ge18M (M = Cu, Ag, Au): metalloid cluster compounds as unusual building blocks for a supramolecular chemistry

Cited by 103 publications

References 36 publications

Coordination of Tri-Substituted Nona–Germanium Clusters to Cu(I) and Pd(0)

Coordination of Tri-Substituted Nona–Germanium Clusters to Cu(I) and Pd(0)

[Ge12{FeCp(CO)2}8{FeCp(CO)}2]: A Ge12 Core Resembles the Arrangement of the High‐Pressure Modification Germanium (II)

N-Heterocyclic Carbene Coinage Metal Complexes of the Germanium-Rich Metalloid Clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr)3 and RI = Si(TMS)3

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[Ge₁₂{FeCp(CO)₂}₈{FeCp(CO)}₂]: A Ge₁₂ Core Resembles the Arrangement of the High‐Pressure Modification Germanium (II)