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)

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/68378271:_____/25:00637455

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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)

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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)

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/LTAIN19152" target="_blank" >LTAIN19152: Karboranovými ligandy chráněné kovové nanoklastry: nová třída materiálů s atomárním rozlišením</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

Chemical Science

ISSN

2041-6520

e-ISSN

2041-6539

Svazek periodika

16

Číslo periodika v rámci svazku

31

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

13

Strana od-do

14127-14139

Kód UT WoS článku

001525096700001

EID výsledku v databázi Scopus

2-s2.0-105010230524