Hu Chaopeng, Liu Liu Leo
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, China.
Inorg Chem. 2023 Feb 27;62(8):3592-3600. doi: 10.1021/acs.inorgchem.2c04258. Epub 2023 Feb 10.
We show that a tris(carbene)borate (TCB) ligand, namely [PhB(BuIm)] ([PhB(BuIm)] = phenyltris(3--butylimidazol-2-ylidene)borato), is capable of stabilizing an unprecedented nucleophilic Sn(II) cation salt. Unlike known Sn(II) cations, the strong electron-donating ability of [PhB(BuIm)] makes the cationic tin atom electron-rich, σ-donating yet slightly π-accepting, which allows for the ensuing facile oxidation with -chloranil and S as well as coordination with coinage metals. The former oxidations give the Sn(IV) cation salts, while the latter reactions produce the metal complexes. The electronic structures of these species are thoroughly probed by quantum chemical computations. These results uncover an added role for TCB ligands in isolating unprecedented p-block species.
我们表明，一种三（卡宾）硼酸酯（TCB）配体，即[PhB(BuIm)]（[PhB(BuIm)] = 苯基三（3-丁基咪唑-2-亚基）硼酸根），能够稳定一种前所未有的亲核Sn(II)阳离子盐。与已知的Sn(II)阳离子不同，[PhB(BuIm)]的强给电子能力使阳离子锡原子富电子，具有σ给电子能力但略带π接受能力，这使得随后能与四氯苯醌和硫轻松发生氧化反应以及与贵金属配位。前者的氧化反应生成Sn(IV)阳离子盐，而后者的反应生成金属配合物。通过量子化学计算对这些物种的电子结构进行了深入探究。这些结果揭示了TCB配体在分离前所未有的p区物种方面的额外作用。
