School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington, 6012, New Zealand.
Chemistry. 2019 Nov 7;25(62):14183-14191. doi: 10.1002/chem.201903175. Epub 2019 Oct 9.
The bis(amidodimethyl)disiloxane antimony chlorides Sb(NON )Cl (NON =[O(SiMe NR) ] ; R=tBu, Ph, 2,6-Me C H =Dmp, 2,6-iPr C H =Dipp, 2,6-(CHPh ) -4-tBuC H =tBu-Bhp) are reduced to Sb and Sb species by using Mg reagents, [Mg(BDI )] (BDI=[HC{C(Me)NR'} ] ; R'=2,4,6-Me C H =Mes, Dipp). Stoichiometric reactions with Sb(NON )Cl (R=tBu, Ph) form dimeric Sb stibanes [Sb(NON )] , shown crystallographically to contain Sb-Sb single bonds. The analogous distibane with R=Dmp substituents has an exceptionally long Sb-Sb interaction and exhibits spectroscopic and reactivity properties consistent with radical character in solution. When R=Dipp, reductions with Mg reagents directly give distibenes [Sb(μ-NON )Mg(BDI )(THF) ] (R'=Mes, n=1; R'=Dipp, n=0). Crystallographic analysis shows a trans-substitution of the Sb=Sb double bond, with bridging NON -ligands between the Sb and Mg centres. An attempt to access the NON -analogue using the same protocol afforded the polystibide cluster Sb [μ ,η -Mg(BDI )] , which co-crystallized with the ligand transfer product, [Mg(BDI )] (μ-NON ).
双（氨甲基二甲基）二硅氧烷锑氯化物 Sb（NON）Cl（NON=[O（SiMeNR）]；R=tBu、Ph、2,6-MeC6H=Dmp、2,6-iPrC6H=Dipp、2,6-（CHPh）-4-tBuC6H=tBu-Bhp）可通过使用镁试剂[Mg（BDI）]（BDI=[HC{C（Me）NR'}]；R'=2,4,6-MeC6H=Mes、Dipp）还原为 Sb 和 Sb 物种。与 Sb（NON）Cl（R=tBu、Ph）的化学计量反应形成二聚 Sb 次膦烷[ Sb（NON）]，晶体结构显示其含有 Sb-Sb 单键。具有 R=Dmp 取代基的类似二膦烷具有异常长的 Sb-Sb 相互作用，并表现出与溶液中自由基特征一致的光谱和反应性。当 R=Dipp 时，镁试剂的还原直接生成二膦烷[ Sb（μ-NON）Mg（BDI）（THF）]（R'=Mes，n=1；R'=Dipp，n=0）。晶体结构分析表明 Sb=Sb 双键的反式取代，Sb 和 Mg 中心之间存在桥接 NON-配体。尝试使用相同的方案获得 NON 类似物，得到了多锑化物簇 Sb[μ，η-Mg（BDI）]，它与配体转移产物[Mg（BDI）]（μ-NON）共结晶。
