Zhu Qihao, Fettinger James C, Power Philip P
Department of Chemistry, University of California, Davis, California 95616, USA.
Dalton Trans. 2021 Sep 21;50(36):12555-12562. doi: 10.1039/d1dt02473f.
Reaction of the aryltin(II) hydrides {ArSn(μ-H)} or {ArSn(μ-H)} (Ar = -CH-2,6-(CH-2,6-Pr), Ar = -CH-2,6-(CH-2,4,6-Pr)) with two equivalents of the molybdenum carbonyl [Mo(CO)(THF)] afforded the divalent tin hydride transition metal complexes, Mo(CO){Sn(Ar)H}, (1), or Mo(CO){Sn(Ar)(THF)H} (2), respectively. Complex 1 effects the facile hydrostannylation of carbon dioxide, to yield Mo(CO){Sn(Ar)(κ-O,O'-OCH)}, (3), which features a bidentate formate ligand coordinating the tin atom. Reaction of 3 with the pinacolborane, HBpin (pin = pinacolato) in benzene regenerated 1 in quantitative yield. All complexes were characterized by X-ray crystallography, as well as UV-visible, IR, and multinuclear NMR spectroscopies. The isolation of 1 and 2 is consistent with the existence of monomeric forms of {ArSn(μ-H)} and {ArSn(μ-H)} in solution. Regeneration of 1 from 3 reaction with pinacolborane as the hydrogen source shows the catalytic potential of 1 in the hydrogenation of CO.
芳基氢化锡（II）{ArSn(μ-H)}或{ArSn(μ-H)}（Ar = -CH-2,6-(CH-2,6-Pr)，Ar = -CH-2,6-(CH-2,4,6-Pr)）与两当量的羰基钼[Mo(CO)(THF)]反应，分别得到二价氢化锡过渡金属配合物Mo(CO){Sn(Ar)H}（1）或Mo(CO){Sn(Ar)(THF)H}（2）。配合物1能使二氧化碳顺利进行氢锡化反应，生成Mo(CO){Sn(Ar)(κ-O,O'-OCH)}（3），其特征是一个双齿甲酸酯配体与锡原子配位。3与频哪醇硼烷HBpin（pin = 频哪醇酯）在苯中反应，能以定量产率再生1。所有配合物均通过X射线晶体学以及紫外可见光谱、红外光谱和多核核磁共振光谱进行了表征。1和2的分离与{ArSn(μ-H)}和{ArSn(μ-H)}在溶液中以单体形式存在相一致。以频哪醇硼烷作为氢源，3反应再生1，这表明1在CO氢化反应中具有催化潜力。
