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)

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F25%3A00637455" target="_blank" >RIV/61388980:_____/25:00637455 - isvavai.cz</a>

Alternative codes found

RIV/68378271:_____/25:00637455

Result on the web

<a href="https://hdl.handle.net/11104/0368684" target="_blank" >https://hdl.handle.net/11104/0368684</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d5sc03562g" target="_blank" >10.1039/d5sc03562g</a>

Result language

angličtina

Original language name

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)

Original language description

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<middle dot>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)}2(mu 3-S)6(mu 3-O)2] (1) and hexacapped trigonal bipyramidal [(Cp*Ti)4{Ti(1,2-(S)2-1,2-C2B10H10)}(mu 3-S)6] (2) clusters. One of the driving forces of these reactions is the cleavage of C-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-B bond formation that yielded a kappa 2-hydridoborato complex, [(Cp*Ti){kappa 2-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.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

<a href="/en/project/LTAIN19152" target="_blank" >LTAIN19152: Carborane-protected metal nanoclusters: A new family of materials with atomic precision</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2025

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Chemical Science

ISSN

2041-6520

e-ISSN

2041-6539

Volume of the periodical

16

Issue of the periodical within the volume

31

Country of publishing house

GB - UNITED KINGDOM

Number of pages

13

Pages from-to

14127-14139

UT code for WoS article

001525096700001

EID of the result in the Scopus database

2-s2.0-105010230524