All-metallagermoxane with an adamantanoid cage structure: [(Cp*Ru(CO)₂Ge)₄(μ-O)₆] (Cp* = η⁵-C₅Me₅)

Abstract

In an attempt to synthesize a zero valent germanium compound, we have carried out the reaction of [(Cp*RuCO)(GeCl2)]2, 1 with potassium metal that led to the formation of a metallagermoxane [(Cp*Ru(CO)2Ge)4(μ-O)6], 2. Compound 2 is the first example of a tetrametallagermoxane with an exo-{Cp*Ru(CO)2} fragment. DFT calculations were used to examine the key intermediates associated with the formation of 2.

N-Heterocyclic Carbene-Stabilized Germa-acylium Ion: Reactivity and Utility in Catalytic CO2 Functionalizations

“…In the solid-state IR spectrum, compound 3 displays a strong absorption at 807 cm –1 which is assigned as GeO. This is blue-shifted compared to the reported GeO stretching in Eind 2 GeO (917 cm –1 ) and red-shifted in comparison to the Ge–O single bond stretching frequency (769 cm –1 ) . Thus, structural and IR data suggest a strong dominance of a zwitterionic resonance form ( 3a + , Scheme ) in the ground state.…”

“…This is blue-shifted compared to the reported GeO stretching in Eind 2 GeO (917 cm −1 ) and red-shifted in comparison to the Ge−O single bond stretching frequency (769 cm −1 ). 54 Thus, structural and IR data suggest a strong dominance of a zwitterionic resonance form (3a + , Scheme 1) in the ground state. The calculated structure of 3 + is in good agreement with the experimental structure (calculated IR 800.8 cm −1 ).…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[335] A reaction more closely related to the synthesis of the higher chalcogenide congeners is utilized for [{(Me3Si)3CSn}4O6] (627), which is made by combining (Me3Si)3CSnCl3 with Na2O. [317] Two further examples obtained from hydrolysis are stabilized by transition metal fragments (628-629), [336,337] with the last one being a cationic species [{Sn(DMEGqu)Br}4O4(OH)2]Br2 (630, DMEGqu = N-(1,3-dimethylimidazolidin2-ylidene)quinoline-8amine) formed by SnBr4, DMEGqu and H2O and exhibiting a coordination number of 6 at the Sn center, unusual for adamantane-type structures. [338] Chemical Science Accepted Manuscript Please do not adjust margins Please do not adjust margins [304,305] [(EtSi)4S6] (566)…”

Ruthenium and Osmium Germyl Complexes Derived from the Reactions of MXCl(PPh3)3 (M = Ru, Os; X = Cl, H) with Terphenylchlorogermylene (C6H3‐2,6‐Trip2)GeCl (Trip = 2,4,6‐iPr3C6H2)

“…Closely related to germylene and germylyne complexes are transition‐metal germyl complexes, which have been known for a long time and have continuously received considerable attention over the last several decades, mainly because of their relevance to the catalytic transformations involving germanium, and materials chemistry. [12a], The most versatile methods for the synthesis of transition‐metal germyl complexes involve either oxidative addition of the Ge–X bond GeXR 3 (X = H, Cl)[12a], or insertion of dihalogen species GeX 2 into the M–X bond[12a], [13a], , to give triorgano M‐GeR 3 or trihalogen M‐GeX 3 germyl derivatives.…”

“…[12a], The most versatile methods for the synthesis of transition‐metal germyl complexes involve either oxidative addition of the Ge–X bond GeXR 3 (X = H, Cl)[12a], or insertion of dihalogen species GeX 2 into the M–X bond[12a], [13a], , to give triorgano M‐GeR 3 or trihalogen M‐GeX 3 germyl derivatives. However, despite of the large number of germyl complexes of transition metals that have been prepared in recent years, ruthenium germyl complexes are still much less common,[13a], [15c], , , while the osmium congeners are even more limited , , , …”