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Bis(silylene)-Stabilized Monovalent Nitrogen Complexes.

ABSTRACT: The first series of bis(silylene)-stabilized nitrogen(I) compounds is described. Starting from the 1,2-bis(N-heterocyclic silylenyl) 1,2-dicarba-closo-dedocaborane(12) scaffold 1, [1,2-(LSi)₂ C₂ B₁₀ H₁₀ ; L=PhC(N^t Bu)₂ ], reaction with adamantyl azide (AdN₃ ) affords the terminal N-?₂ -bridged zwitterionic carborane-1,2-bis(silylium) AdN₃ adduct 2 with an open-cage dianionic nido-C₂ B₁₀ cluster core. Remarkably, upon one-electron reduction of 2 with C₈ K and liberation of N₂ and adamantane, the two silylene subunits are regenerated to furnish the isolable bis(silylene)-stabilized N^I complex as an anion of 3 with the nido-C₂ B₁₀ cluster cage. On the other hand, one-electron oxidation of 2 with silver(I) yields the monocationic bis(silylene) N^I complex 4 with the closo-C₂ B₁₀ cluster core. Moreover, the corresponding neutral N^I radical complex 5 results from single-electron transfer from 3 to 4.

SUBMITTER: Yao S

PROVIDER: S-EPMC7756627 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

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Bis(silylene)-Stabilized Monovalent Nitrogen Complexes.

Yao Shenglai S Szilvási Tibor T Xiong Yun Y Lorent Christian C Ruzicka Ales A Driess Matthias M

Angewandte Chemie (International ed. in English) 20200928 49

The first series of bis(silylene)-stabilized nitrogen(I) compounds is described. Starting from the 1,2-bis(N-heterocyclic silylenyl) 1,2-dicarba-closo-dedocaborane(12) scaffold 1, [1,2-(LSi)2 C2 B10 H10 ; L=PhC(Nt Bu)2 ], reaction with adamantyl azide (AdN3 ) affords the terminal N-μ2 -bridged zwitterionic carborane-1,2-bis(silylium) AdN3 adduct 2 with an open-cage dianionic nido-C2 B<su ...[more]

PMID: 32841449

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Project description:Manganese disilyl hydride complexes [(dmpe)2MnH(SiH2R)2] (4Ph : R = Ph, 4Bu : R = n Bu) reacted with ethylene to form silene hydride complexes [(dmpe)2MnH(RHSi[double bond, length as m-dash]CHMe)] (6Ph,H : R = Ph, 6Bu,H : R = n Bu). Compounds 6R,H reacted with a second equivalent of ethylene to generate [(dmpe)2MnH(REtSi[double bond, length as m-dash]CHMe)] (6Ph,Et : R = Ph, 6Bu,Et : R = n Bu), resulting from apparent ethylene insertion into the silene Si-H bond. Furthermore, in the absence of ethylene, silene complex 6Bu,H slowly isomerized to the silylene hydride complex [(dmpe)2MnH([double bond, length as m-dash]SiEt n Bu)] (3Bu,Et ). Reactions of 4R with ethylene likely proceed via low-coordinate silyl {[(dmpe)2Mn(SiH2R)] (2Ph : R = Ph, 2Bu : R = n Bu)} or silylene hydride {[(dmpe)2MnH([double bond, length as m-dash]SiHR)] (3Ph,H : R = Ph, 3Bu,H : R = n Bu)} intermediates accessed from 4R by H3SiR elimination. DFT calculations and high temperature NMR spectra support the accessibility of these intermediates, and reactions of 4R with isonitriles or N-heterocyclic carbenes yielded the silyl isonitrile complexes [(dmpe)2Mn(SiH2R)(CNR')] (7a-d: R = Ph or n Bu; R' = o-xylyl or t Bu), and NHC-stabilized silylene hydride complexes [(dmpe)2MnH{[double bond, length as m-dash]SiHR(NHC)}] (8a-d: R = Ph or n Bu; NHC = 1,3-diisopropylimidazolin-2-ylidene or 1,3,4,5-tetramethyl-4-imidazolin-2-ylidene), respectively, all of which were crystallographically characterized. Silyl, silylene and silene complexes in this work were accessed via reactions of [(dmpe)2MnH(C2H4)] (1) with hydrosilanes, in some cases followed by ethylene. Therefore, ethylene (C2H4 and C2D4) hydrosilylation was investigated using [(dmpe)2MnH(C2H4)] (1) as a pre-catalyst, resulting in stepwise conversion of primary to secondary to tertiary hydrosilanes. Various catalytically active manganese-containing species were observed during catalysis, including silylene and silene complexes, and a catalytic cycle is proposed.

Dataset Information

Bis(silylene)-Stabilized Monovalent Nitrogen Complexes.

Publications

Bis(silylene)-Stabilized Monovalent Nitrogen Complexes.

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