The synthesis of a bicyclic germylene from the reaction of a germole dianion with hafnocene dichloride is reported. This germylene is stabilized by a homoconjugative interaction of the dicoordinated germanium atom with a remote C=C double bond. First reactivity studies revealed its nucleophilic character and resulted in the synthesis of bimetallic hafnium/iron and hafnium/tungsten complexes with a germylene group linker.
We present the insertion behavior of the alkyl-substituted germylene Ge(Flu) in different E-X σ bonds (E = Au, Si, Ge, Sn), first with the isolation of the germylgold complex (Flu)Ge(Cl)AuPPh. Afterward, the oxidative addition of GeCl to Ge(Flu) gives the digermane (Flu)Ge(Cl)GeCl, followed by a reductive elimination of GeCl and the formation of the oxidation product (Flu)GeCl. A comparable behavior is observed, with the homologues ECl (E = Si, Sn) stopping at different steps of the reaction.
Catalysis using low-valent main-group compounds is usually done under inert conditions; no example of such catalysis has been doable entirely in ambient conditions until now. This aspect is addressed in this work through an air- and water-stable germylene cation [DPMGe][(OH)B(CF)] (2) (DPM=dipyrromethene); it efficiently catalyzes aldehyde and ketone hydrosilylations under ambient conditions. Detailed theoretical studies reveal that compound 2's stability is bolstered by the interaction between the anion and germanium's frontier orbitals.
Introducing phospha-bicyclohexene (BCH)-germylenes (BCHGe's) as a novel, multifunctional compound class: the title compounds 15-18 are obtained from simple salt metathesis reactions of dipotassium germacyclopentadienediides K[1] with phosphorusdichlorides. The BCHGe's 15-18 are stabilized by homoconjugation of the germanium(ii) centre with the remote C[double bond, length as m-dash]C double bond. Despite substantial thermodynamic stabilization, phospha-BCHGe's are reactive and undergo a reductive elimination of elemental germanium to give the corresponding phospholes.
State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China.
This study describes the synthesis, structural characterization, and catalytic application of a bis(germylene)-stabilized stannylone (). The reduction of digermylated stannylene () with 2.2 equiv of potassium graphite (KC) leads to the formation of stannylone as a green solid in 78% yield.
The aminotroponiminate (ATI) ligand stabilized germylene cation [(i-Bu)ATIGe][B(CF)] (2) is found to be an efficient low-valent main-group catalyst for the cyanosilylation of aldehydes and ketones (ATI=aminotroponiminate). It was synthesized by reacting [(i-Bu)ATIGeCl] (1) with Na[B(CF)]. The catalytic cyanosilylation of diverse aliphatic and aromatic carbonyl compounds (aldehydes and ketones) using 0.
