Reaction of carbene-stabilized disilicon (1) with the lithium-based dithiolene radical (2 ) affords the first dianionic silicon tris(dithiolene) complex (3). Notably, the formation of 3 represents the unprecedented utilization of carbene-stabilized disilicon (1) as a silicon-transfer agent. The nature of 3 was probed by multinuclear NMR spectroscopy, single-crystal X-ray diffraction, and DFT computations.
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Carbene-Stabilized Disilicon as a Silicon-Transfer Agent: Synthesis of a Dianionic Silicon Tris(dithiolene) Complex.
Angew Chem Int Ed Engl
June 2020
Department of Chemistry and the Center for Computational Chemistry, The University of Georgia, Athens, GA, 30602-2556, USA.
Reaction of carbene-stabilized disilicon (1) with the lithium-based dithiolene radical (2 ) affords the first dianionic silicon tris(dithiolene) complex (3). Notably, the formation of 3 represents the unprecedented utilization of carbene-stabilized disilicon (1) as a silicon-transfer agent. The nature of 3 was probed by multinuclear NMR spectroscopy, single-crystal X-ray diffraction, and DFT computations.
View Article and Find Full Text PDFPush-Pull Stabilization of Parent Monochlorosilylenes.
J Am Chem Soc
August 2016
Department of Chemistry and the Center for Computational Chemistry, The University of Georgia, Athens, Georgia 30602-2556, United States.
While reaction of carbene-stabilized disilicon L:Si═Si:L (L: = C{N(2,6-(i)Pr2C6H3)CH}2) (8) with HCl·NC5H5 results in carbene-stabilized Si2Cl2 (2) and substituted 1H-imidazole (9), combination of the corresponding Fe(CO)4-modified disilicon carbene complex L:Si═Si[Fe(CO)4]:L (6) with pyridine hydrochloride gives a species containing two push-pull-stabilized parent monochlorosilylenes that are bridged by an Fe(CO)3 unit (7). The nature of 7 was further elucidated by spectroscopic, crystallographic, and computational methods. Spectroscopic data suggest that 7 exists as two diastereoisomers.
View Article and Find Full Text PDFAddition of Small Electrophiles to N-Heterocyclic-Carbene-Stabilized Disilicon(0): A Revisit of the Isolobal Concept in Low-Valent Silicon Chemistry.
J Am Chem Soc
April 2016
Institute of Inorganic Chemistry, University of Bonn, Gerhard-Domagk-Straße 1, D-53121 Bonn, Germany.
Protonation and alkylation of (Idipp)Si═Si(Idipp) (1) afforded the mixed-valent disilicon(I)-borates [(Idipp)(R)Si(II)═Si(0)(Idipp)][B(Ar(F))4] (1R[B(Ar(F))4]; R = H, Me, Et; Ar(F) = C6H3-3,5-(CF3)2; Idipp = C[N(C6H3-2,6-iPr2)CH]2) as red to orange colored, highly air-sensitive solids, which were characterized by single-crystal X-ray diffraction, IR spectroscopy and multinuclear NMR spectroscopy. Dynamic NMR studies in solution revealed a degenerate isomerization (topomerization) of the "σ-bonded" tautomers of 1H[B(Ar(F))4], which proceeds according to quantum chemical calculations via a NHC-stabilized (NHC = N-heterocyclic carbene) disilahydronium ion ("π-bonded" isomer) and is reminiscent of the degenerate rearrangement of carbenium ions formed upon protonation of olefins. The topomerization of 1H[B(Ar(F))4] provides the first example of a reversible 1,2-H migration along a Si═Si bond observed in a molecular system.
View Article and Find Full Text PDFSynthesis of an N-Heterocyclic-Carbene-Stabilized Siladiimide.
Inorg Chem
January 2016
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
The reaction of the N-heterocyclic-carbene-stabilized disilicon(0) complex [IPr→Si═Si←IPr] (1; IPr = :C{N(Ar)CH}2 and Ar = 2,6-iPr2C6H3) with ArN3 afforded the N-heterocyclic-carbene-stabilized siladiimide [ArNSi(IPr)NAr] (2). X-ray crystallography and theoretical studies show that the N-Si-N skeleton in compound 2 possesses considerable double-bond character and the Si atom is stabilized by the N-heterocyclic carbene.
View Article and Find Full Text PDFStabilization of Silicon-Carbon Mixed Oxides.
J Am Chem Soc
July 2015
Department of Chemistry and the Center for Computational Chemistry, The University of Georgia, Athens, Georgia 30602-2556, United States.
The first carbene-stabilized silicon-carbon mixed oxide, (SiO2)2CO2 (4), was synthesized by CO2 oxidation of either carbene-stabilized disilicon, L:Si═Si:L (L: = :C{N(2,6-Pr(i)2C6H3)CH}2) (1), or carbene-stabilized Si2O3 (2) (which can be obtained via N2O oxidation of 1). The structure and bonding of 4 was probed by both experimental and computational methods.
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