Directed Syntheses of CS(2)- and CS(3)-Bridged Decaborane-14 Analogues

• Published in: Inorganic chemistry 2021-08, Vol.60 (16), p.12367-12376
• Main Authors: Nandi, Chandan, Kar, Ketaki, Gayen, Sourav, Roisnel, Thierry, Ghosh, Sundargopal
• Format: Article
• Language: English
• Subjects: Chemical Sciences
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.1c01585

To establish a procedure for single-cage cluster expansion of open cage dimetallaoctaboranes(12), we have investigated the chemistry of -[(Cp*M)BH] (η-CMe = Cp*, : M = Co; : M = Rh), with diverse chalcogen-based borate ligands. As a result, treatment of - and - with Li[BHE] (E = S, Se, or Te) yielded 10-vertex -[(Cp*Co)BEH] (: E = S; : E = Se; : E = Te) along with known 10-vertex -[(Cp*M)BHE] (: E = S, M = Co; : E = Se, M = Co; : E = Te, M = Co; : E = Se, M = Rh). The geometries of dimetallachalcogenaboranes, -, are isostructural with decaborane(14). Thermolysis of - and - with an intermediate, generated from CS and [LiBH]·THF reaction in THF, produced -[(Cp*M)BSH(CHS)] (: M = Co; : M = Rh) and -[(Cp*M)BSH(CS)] (: M = Co; : M= Rh). Clusters - are rare species in which one of the B-B bonds is coordinated with a {CS} or {CS} ligand, generating di(thioborolane) {BSCH} or di(thioboralane)-thione {BCS} moieties. To examine further the coordination chemistry of CS-bridged decaborane(14) analogue , photolysis was carried out with {M(CO)·THF} (M = Mo or W) that led to the isolation of [(Cp*Co)BSH(CHS){M(CO)}] (: M = Mo; : M = W), where the {CHS} moiety is coordinated with one {M(CO)} moiety in η-fashion. All the synthesized clusters have been characterized by ESI-mass, multinuclear NMR spectroscopy, and IR spectroscopy and structurally solved by single-crystal XRD. Furthermore, DFT calculations probe the bonding of these CS- and CS-bridged decaborane analogues.