Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720-1460 (USA).
Angew Chem Int Ed Engl. 2015 May 26;54(22):6622-6. doi: 10.1002/anie.201502156. Epub 2015 Apr 2.
Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2 Ru-Sn-Trip] (1; IXy=1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; Cp*=η(5) -C5 Me5 ; Trip=2,4,6-iPr3 C6 H2 ) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β-unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip] (2) and [Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip] (3), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin-substituted ketene complex [Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip] (4), which is most likely a decomposition product from the putative ruthenium-substituted stannene complex. The isolation of a ruthenium-substituted stannene [Cp*(IXy)(H)2 RuSn(=Flu)Trip] (5) and stanna-imine [Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip] (6) complexes was achieved by treatment of 1 with 9-diazofluorene and tosyl azide, respectively.
[Cp*(IXy)(H)2 Ru-Sn-Trip]（1；IXy=1,3-双（2,6-二甲基苯基）咪唑-2-亚基；Cp*=η(5) -C5 Me5 ；Trip=2,4,6-iPr3 C6 H2 ）与各种有机底物的反应性研究。复合物 1 与安息香和α,β-不饱和酮反应，发生[1+4]环加成反应，生成[Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip]（2）和[Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip]（3）。1 与重氮乙酸乙酯反应生成锡取代的酮烯络合物[Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip]（4），这很可能是假定的钌取代锡烯络合物的分解产物。通过用 9-重氮芴和对甲苯磺酰叠氮处理 1，分别分离得到了钌取代的锡烯[Cp*(IXy)(H)2 RuSn(=Flu)Trip]（5）和锡亚胺[Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip]（6）络合物。
