Garg Palak, Dange Deepak, Jiang Yixiao, Jones Cameron
School of Chemistry, PO Box 23, Monash University, VIC, 3800, Australia.
Dalton Trans. 2022 May 24;51(20):7838-7844. doi: 10.1039/d2dt00721e.
Reactions of the known amidinate stabilised 1,2-disilylene, [{ArC(NDip)}Si]1 (Dip = 2,6-diisopropylphenyl, Ar = 4-CHBu) with a series of inert, unsaturated small molecule substrates have been carried out. Compound 1 reduces BuNC: to give the singlet biradicaloid 1,3-disilacyclobutanediyl [{ArC(NDip)}Si(μ-CNBu)]3, which can be oxidised by 1,2-dibromoethane to give [{ArC(NDip)}(Br)Si(μ-CNBu)]4. Disilylene 1 reduces two molecules of ethylene to give an unprecedented disilabicyclo[2.2.0]hexane, [{ArC(NDip)}Si(μ-CH)]5. In contrast, only one molecule of ethylene inserts in the Ge-Ge bond of the digermylene analogue of 1, [{ArC(NDip)}Ge]6, leading to the formation of the bis(germylene), {ArC(NDip)}Ge 7. Compound 1 reduces CO, generating CO, and the oxo/carbonate-bridged disilicon(IV) system, {ArC(NDip)}Si(μ-CO)(μ-O)Si{(NDip)CAr} 10, while its reaction with NO proceeds generation of N, and a hydrogen abstraction process, to give the oxo/hydroxy disilicon(IV) species, [{ArC(NDip)}(HO)Si(μ-O)]11. This study highlights new small molecule activation chemistry for 1,2-disilylenes, which could lead to further adoption of compound 1 as a potent reducing reagent for the transformation of inert unsaturated molecules into value added products.
已对已知的脒基稳定的1,2 - 二硅烯[{ArC(NDip)}Si]1（Dip = 2,6 - 二异丙基苯基，Ar = 4 - CHBu）与一系列惰性不饱和小分子底物的反应进行了研究。化合物1将丁腈还原为单线态双自由基类的1,3 - 二硅环丁二烯[{ArC(NDip)}Si(μ - CNBu)]3，该物质可被1,2 - 二溴乙烷氧化得到[{ArC(NDip)}(Br)Si(μ - CNBu)]4。二硅烯1将两分子乙烯还原得到前所未有的二硅双环[2.2.0]己烷[{ArC(NDip)}Si(μ - CH)]5。相比之下，乙烯仅一分子插入1的二锗烯类似物[{ArC(NDip)}Ge]6的Ge - Ge键中，导致双（锗烯）[{ArC(NDip)}Ge](μ - CH) 7的形成。化合物1还原CO，生成CO以及氧代/碳酸酯桥联的二硅（IV）体系{ArC(NDip)}Si(μ - CO)(μ - O)Si{(NDip)CAr} 10，而其与NO的反应进行氮的生成以及氢原子提取过程，得到氧代/羟基二硅（IV）物种[{ArC(NDip)}(HO)Si(μ - O)]11。这项研究突出了1,2 - 二硅烯新的小分子活化化学，这可能导致化合物1进一步被用作将惰性不饱和分子转化为高附加值产品的有效还原剂。
