{Ge9R3Cr(CO)5}− and {Ge9R3Cr(CO)3}−: a metalloid cluster (Ge9R3−) as a flexible ligand in coordination chemistry [R = Si(SiMe3)3]

Schenk, Christian; Schnepf, Andreas

doi:10.1039/b901870k

Cited by 76 publications

(69 citation statements)

References 30 publications

(13 reference statements)

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“…It is slightly off the threefold axis and generates three positions, each with 1/3 occupancy. [50] Furthermore, similar positioning of the Sn atom as exo-bonded to one vertex but also tilted towards the trigonal base has been observed before in the monosubstituted Ge 9 and Sn 9 clusters [Ge 9 SnPh 3 ] 3À and [Sn 9 SnCy 3 ] 3À . Furthermore, the germanium atoms forming the capped triangular base exhibited thermal ellipsoids elongated tangentially towards the Sn atom.…”

Section: Feng LI Alvaro Muçoz-castro and Slavi C Sevov*supporting

confidence: 73%

[Ge₉{Si(SiMe₃)₃}₃{SnPh₃}]: A Tetrasubstituted and Neutral Deltahedral Nine‐Atom Cluster

Muñoz-Castro

Sevov

2012

Angew Chem Int Ed

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Section: Feng LI Alvaro Muçoz-castro and Slavi C Sevov*supporting

confidence: 73%

[Ge₉{Si(SiMe₃)₃}₃{SnPh₃}]: A Tetrasubstituted and Neutral Deltahedral Nine‐Atom Cluster

Muñoz-Castro

Sevov

2012

Angew Chem Int Ed

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“…[20] Such À (M = Cr, Mo, W) [21,22] and in the transition-metal linked nineteen-atom cluster cores within [MGe 18 {Si(SiMe 3 ) 3 } 6 ]…”

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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“…[ [16][17][18][19][20] It is informative to compare the [E 9 Ir(cod)] 3-clusters would give E 9 Ir 3-binary complexes, which would presumably have 20-electron closo structure with two fewer electrons than the Cu@E 9 3-systems. Attempts to remove the COD ligands are in progress.…”

Section: Solid-state Structuresmentioning

confidence: 99%

The closo‐[Sn₉Ir(cod)]^3– and [Pb₉Ir(cod)]^3– Zintl Ions: Isostructural Ir^I Derivatives of the nido‐E₉^4– Anions (E = Sn, Pb)

2010

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{Ge9R3Cr(CO)5}− and {Ge9R3Cr(CO)3}−: a metalloid cluster (Ge9R3−) as a flexible ligand in coordination chemistry [R = Si(SiMe3)3]

Abstract: The reactions of the metalloid cluster {Ge9[Si(SiMe3)3]3}- with Cr(CO)5COE (COE=cyclooctene) and Cr(CO)3(CH3CN)3 lead to the new cluster compounds {Ge9[Si(SiMe3)3]3Cr(CO)5}- and {Ge9[Si(SiMe3)3]3Cr(CO)3}-, whose structural and electronic properties are presented.

Cited by 76 publications

References 30 publications

[Ge₉{Si(SiMe₃)₃}₃{SnPh₃}]: A Tetrasubstituted and Neutral Deltahedral Nine‐Atom Cluster

[Ge₉{Si(SiMe₃)₃}₃{SnPh₃}]: A Tetrasubstituted and Neutral Deltahedral Nine‐Atom Cluster

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

The closo‐[Sn₉Ir(cod)]^3– and [Pb₉Ir(cod)]^3– Zintl Ions: Isostructural Ir^I Derivatives of the nido‐E₉^4– Anions (E = Sn, Pb)

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{Ge9R3Cr(CO)5}− and {Ge9R3Cr(CO)3}−: a metalloid cluster (Ge9R3−) as a flexible ligand in coordination chemistry [R = Si(SiMe3)3]

Abstract: The reactions of the metalloid cluster {Ge9[Si(SiMe3)3]3}- with Cr(CO)5COE (COE=cyclooctene) and Cr(CO)3(CH3CN)3 lead to the new cluster compounds {Ge9[Si(SiMe3)3]3Cr(CO)5}- and {Ge9[Si(SiMe3)3]3Cr(CO)3}-, whose structural and electronic properties are presented.

Cited by 76 publications

References 30 publications

[Ge9{Si(SiMe3)3}3{SnPh3}]: A Tetrasubstituted and Neutral Deltahedral Nine‐Atom Cluster

[Ge9{Si(SiMe3)3}3{SnPh3}]: A Tetrasubstituted and Neutral Deltahedral Nine‐Atom Cluster

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

The closo‐[Sn9Ir(cod)]3– and [Pb9Ir(cod)]3– Zintl Ions: Isostructural IrI Derivatives of the nido‐E94– Anions (E = Sn, Pb)

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[Ge₉{Si(SiMe₃)₃}₃{SnPh₃}]: A Tetrasubstituted and Neutral Deltahedral Nine‐Atom Cluster

[Ge₉{Si(SiMe₃)₃}₃{SnPh₃}]: A Tetrasubstituted and Neutral Deltahedral Nine‐Atom Cluster

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

The closo‐[Sn₉Ir(cod)]^3– and [Pb₉Ir(cod)]^3– Zintl Ions: Isostructural Ir^I Derivatives of the nido‐E₉^4– Anions (E = Sn, Pb)