@article {171, title = {Cluster versus coordination: the chemistry of cyclopentadienyl titanium and vanadium complexes with B- and C-functionalized carborane-thiols, [C2B10H12-n(SH)n] (n = 2 or 3)}, journal = {Chemical Science}, year = {2025}, month = {07/2025}, type = {Full article}, abstract = {

A series of B- and C-functionalized di- and trithiol chelating o-carborane ligands have been employed to explore the coordination chemistry with cyclopentadienyl titanium and vanadium complexes. Treatment of [Cp*TiCl3] with [LiBH4{\textperiodcentered}THF], followed by thermolysis with a C-functionalized carborane-dithiol ligand [1,2-(SH)2-1,2-C2B10H10], yielded octacapped octahedral [(Cp*Ti)4{Ti(1,2-(S)2-1,2-C2B10H10)}23-S)63-O)2] (1) and hexacapped trigonal bipyramidal [(Cp*Ti)4{Ti(1,2-(S)2-1,2-C2B10H10)}(μ3-S)6] (2) clusters. One of the driving forces of these reactions is the cleavage of C{\textendash}S bonds of carborane-dithiols that resulted in sulfide ligands and subsequently generated clusters 1 and 2. In contrast, a similar reaction with a B-functionalized carborane-dithiol [9,12-(SH)2-1,2-C2B10H10] led to B{\textendash}B bond formation that yielded a κ2-hydridoborato complex, [(Cp*Ti){κ2-BH3(9,12-(S)2-1,2-C2B10H10)}] (3). To the best of our knowledge, complex 3 is the first example of a carborane-dithiol functionalized hydridoborato complex. Interestingly, when the reactions of [Cp*TiCl3] or [Cp2TiCl2] were carried out with a B-functionalized carborane-trithiol, [8,9,12-(SH)3-1,2-C2B10H9], they led to coordination complexes, [(Cp/Cp*Ti){8,9,12-(S)3-1,2-C2B10H9}] (Cp* (4a) and Cp (4b)). Similarly, when [(Cp*VCl2)3] was employed as a metal precursor, deboronation was observed at the icosahedral cage that resulted in a zwitterionic complex, [(Cp*V){1,5,6-(S)3-nido-7,8-C2B9H9}] (5). All the clusters have been characterized by NMR, IR, mass spectrometry, and X-ray diffraction analysis. Furthermore, the theoretical analyses provided valuable insights into the electronic structures of these unusual clusters.

}, doi = {https://doi.org/10.1039/D5SC03562G}, url = {https://pubs.rsc.org/en/content/articlelanding/2025/sc/d5sc03562g}, author = {Subhash Bairagi and Deepak Kumar Patel and Debipada Chatterjee and Monika Kucerakova and Jan Machacek and Tomas Base and Thalappil Pradeep and Sundargopal Ghosh} }