Molecular structure of decamethylgermanocene in the solid state

Schöpper, Annika; Saak, Wolfgang; Weidenbruch, Manfred

doi:10.1016/j.jorganchem.2005.10.024

Cited by 14 publications

(12 citation statements)

References 10 publications

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“…Cp*Si: + B(Ar F ) 4 – ( 1a ) and Cp*Si: + Al[OC(CF 3 ) 3 ] 4 – ( 1b ) (Table ) were made from decamethylsilicocene ( 3a , Z = Si) by hydride transfer from one of the Cp* residues to the corresponding tritylium salts 4a [X = B(Ar F ) 4 ] and 4b {X = Al[OC(CF 3 ) 3 ] 4 } [see Scheme , method (a)]. This procedure was now successfully applied on the synthesis of new cationic germanium compounds Cp*Ge: + B(Ar F ) 4 – ( 2a ) and Cp*Ge: + Al[OC(CF 3 ) 3 ] 4 – ( 2b ) (see Scheme and Table ) from decamethylgermanocene ( 3a , Z = Ge) . Compounds 2a and 2b were isolated in pure form by crystallization and characterized by NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

“…I. Krossing, University of Freiburg/Germany. GeCl 2 –dioxane complex, decamethylgermanocene ( 3a , Z = Ge), H + (OEt 2 ) 2 B(Ar F ) 4 – , tris(trimethylsilyl)cyclopentadiene, hexakis(trimethylsilyl)germanocene, 1a , and 1b were synthesized according to the literature procedure. H + B(SiCl 3 ) 4 – ( 10 , Bochmann’s acid) was provided by Dr. S. Bochmann, Wacker Chemie AG, Nünchritz, Germany.…”

Section: Methodsmentioning

confidence: 99%

“…1) from decamethylgermanocene (3a, Z = Ge). 18 Compounds 2a and 2b were isolated in pure form by crystallization and characterized by NMR spectroscopy. In addition, the structure of 2a was verified by crystal structure analysis (see Figure 1).…”

Section: ■ Introductionmentioning

confidence: 99%

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Novel Si(II)⁺ and Ge(II)⁺ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction

Fritz‐Langhals

Werge

Kneissl

et al. 2020

Org. Process Res. Dev.

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Novel catalytically active cationic Si(II) and Ge(II) compounds were synthesized and isolated in pure form. The Ge(II)+-based compounds proved to be stable against air and moisture and therefore can be handled very easily. All compounds efficiently catalyze the oxidative coupling of hydrosil(ox)anes with aldehydes and ketones as oxidation reagents and simultaneously the reductive ether coupling at very low amounts of <0.01 mol %. Because the catalysts also catalyze the reversible cyclotrimerization of aldehydes, paraldehyde can be used as a convenient source for acetaldehyde in siloxane coupling. It is shown that the reaction is especially suitable to make siloxane copolymers. Moreover, a new fluorine-free weakly coordinating boronate anion, B(SiCl3)4 –, was successfully combined with the Si(II) and Ge(II) cations to give the stable catalytically active ion pairs Cp*Si:+B(SiCl3)4 –, Cp*Ge:+B(SiCl3)4 –, and [Cp(SiMe3)3Ge:+]B(SiCl3)4 –.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Novel Si(II)⁺ and Ge(II)⁺ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction

Fritz‐Langhals

Werge

Kneissl

et al. 2020

Org. Process Res. Dev.

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“…Precursors of 1 and 2 are the corresponding tetrelocenes 3 and 4, which are made by various organometallic transformations [32][33][34][35].…”

Section: Synthesis and Properties Of Cp-coordinated Cationic Si(ii) + (1) And Ge(ii) + Compounds (2)mentioning

confidence: 99%

Main Group Catalysis: Cationic Si(II) and Ge(II) Compounds as Catalysts in Organosilicon Chemistry

Fritz‐Langhals

2021

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Cyclopentadienyl (Cp)-coordinated cationic Si(II) (1) and Ge(II) compounds (2) are a new class of catalysts for various transformations in organosilicon chemistry. This review demonstrates that these compounds effectively catalyze technically important reactions, such as the hydrosilylation of carbon-carbon multiple bonds and various types of siloxane-coupling reactions, e.g., the Piers-Rubinsztajn reaction and the oxidative siloxane coupling reaction. Whereas the cationic Si(II) compounds are sensitive to air and moisture, the corresponding cationic Ge(II) compounds are bench stable, thus offering further advantages. The new catalysts contribute to the growing need for the substitution of transition metals and heavier main group metals by their lighter congeners, especially in industrially relevant organosilicon chemistry.

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“…In both cases, bent structures were observed indicating that the remaining lone pair is stereochemically active. 41,42 The question of stereochemically active or otherwise lone pairs in lead(II) complexes was also the subject of a paper concerned with lariat ether complexes in which the degree of p-character in the hybridization at lead was linked to the formation of hemidirected geometries. 43 Both rac-and meso-forms of 6 are prepared from the corresponding dilithio salt and tin(II) chloride.…”

Section: Compounds With M(14)-carbon Bondsmentioning

confidence: 99%

Carbon, silicon, germanium, tin and lead

Parr

2007

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Molecular structure of decamethylgermanocene in the solid state

Cited by 14 publications

References 10 publications

Novel Si(II)⁺ and Ge(II)⁺ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction

Novel Si(II)⁺ and Ge(II)⁺ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction

Main Group Catalysis: Cationic Si(II) and Ge(II) Compounds as Catalysts in Organosilicon Chemistry

Carbon, silicon, germanium, tin and lead

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Molecular structure of decamethylgermanocene in the solid state

Cited by 14 publications

References 10 publications

Novel Si(II)+ and Ge(II)+ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction

Novel Si(II)+ and Ge(II)+ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction

Main Group Catalysis: Cationic Si(II) and Ge(II) Compounds as Catalysts in Organosilicon Chemistry

Carbon, silicon, germanium, tin and lead

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Product

Resources

About

Novel Si(II)⁺ and Ge(II)⁺ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction

Novel Si(II)⁺ and Ge(II)⁺ Compounds as Efficient Catalysts in Organosilicon Chemistry: Siloxane Coupling Reaction