The ability of a platinum compound to act as a catalyst for the cyanosilylation of carbonyl compounds is demonstrated through a well-defined germylene stabilized Pt(ii) dicyanide, trans-{(iBu)2ATIGe(iPr)}2Pt(CN)2.
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http://dx.doi.org/10.1039/C8DT00043C | DOI Listing |
Inorg Chem
January 2025
Chemistry Department, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
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.
View Article and Find Full Text PDFChem Asian J
January 2025
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016, India.
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.
View Article and Find Full Text PDFIntroducing 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.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
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.
View Article and Find Full Text PDFChem Asian J
August 2024
Department of Chemistry, Indian Institute of Technology Delhi (IIT Delhi) Hauz Khas, New Delhi, 110016, India.
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.
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