Rajasekharan-Nair Rajeev, Moore Dean, Kennedy Alan R, Reglinski John, Spicer Mark D
Department of Pure and Applied Chemistry, WestChem University of Strathclyde , 295 Cathedral Street, Glasgow G1 1XL, U.K.
Inorg Chem. 2014 Oct 6;53(19):10276-82. doi: 10.1021/ic5013236. Epub 2014 Sep 10.
The chemistry of the hydrotris(mercaptobenzothiazolyl)borate anion (Tbz) with metal salts (HgI2, SbI3, BiI3, CoCl2) is reported in an attempt to probe the stability of the of Tbz ligand once coordinated to hard and soft metals. Complexes of Tbz with bismuth, containing the Bi(Tbz)I3 anion, are stable, but with the other metals this is not the case. Although simple complexes such as [Hg(Tbz)I] and E(Tbz)I3 (E = Sb, Bi) can be isolated from the reaction mixtures, subsequent reactions lead to ligand modification or decomposition. In the presence of mercury and antimony we observe the formation of a hitherto unseen cationic pentacyclic heterocycle. With cobalt we observe a small quantity of a product which suggests a more complete decomposition. A simple benzothiazole (bz) adduct [Co(bz)2Cl2] has been identified, in which the Tbz ligand has disintegrated and the parent heterocycle, mercaptobenzothiazole, has been desulfurized. A rationale for these observations is given.
本文报道了三（巯基苯并噻唑基）硼酸根阴离子（Tbz）与金属盐（HgI₂、SbI₃、BiI₃、CoCl₂）的化学反应，旨在探究Tbz配体与软硬金属配位后的稳定性。Tbz与铋形成的含有[Bi(Tbz)I₃]⁻阴离子的配合物是稳定的，但与其他金属形成的配合物则不然。尽管可以从反应混合物中分离出诸如[Hg(Tbz)I]和[E(Tbz)I₃]⁻（E = Sb、Bi）等简单配合物，但后续反应会导致配体改性或分解。在汞和锑存在的情况下，我们观察到一种前所未见的阳离子五环杂环的形成。对于钴，我们观察到少量产物，这表明发生了更彻底的分解。已鉴定出一种简单的苯并噻唑（bz）加合物[Co(bz)₂Cl₂]，其中Tbz配体已分解，母体杂环巯基苯并噻唑已脱硫。文中给出了这些观察结果的理论依据。
