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Crystallographic Characterization of Ti 2 C 2 @ D 3 h (5)-C 78 , Ti 2 C 2 @ C 3 v (8)-C 82 , and Ti 2 C 2 @ C s (6)-C 82 : Identification of Unsupported Ti 2 C 2 Cluster with Cage-Dependent Configurations.
- Source :
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Inorganic chemistry [Inorg Chem] 2020 Jul 06; Vol. 59 (13), pp. 9416-9423. Date of Electronic Publication: 2020 Jun 17. - Publication Year :
- 2020
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Abstract
- Fullerene cages are ideal hosts to encapsulate otherwise unstable metallic clusters to form endohedral metallofullerenes (EMFs). Herein, a novel Ti <subscript>2</subscript> C <subscript>2</subscript> cluster with two titanium atoms bridged by a C <subscript>2</subscript> -unit has been stabilized by three different fullerene cages to form Ti <subscript>2</subscript> C <subscript>2</subscript> @ D <subscript>3 h </subscript> (5)-C <subscript>78</subscript> , Ti <subscript>2</subscript> C <subscript>2</subscript> @ C <subscript>3 v </subscript> (8)-C <subscript>82</subscript> , and Ti <subscript>2</subscript> C <subscript>2</subscript> @ C <subscript> s </subscript> (6)-C <subscript>82</subscript> , representing the first examples of unsupported titanium carbide clusters. Crystallographic results show that the configuration of the Ti <subscript>2</subscript> C <subscript>2</subscript> cluster changes upon cage variation. In detail, the Ti <subscript>2</subscript> C <subscript>2</subscript> cluster adopts a butterfly shape in Ti <subscript>2</subscript> C <subscript>2</subscript> @ C <subscript>3 v </subscript> (8)-C <subscript>82</subscript> and Ti <subscript>2</subscript> C <subscript>2</subscript> @ C <subscript> s </subscript> (6)-C <subscript>82</subscript> with Ti-C <subscript>2</subscript> -Ti dihedral angles of 156.35 and 147.52° and Ti-Ti distances of 3.633 and 3.860 Å, respectively. In sharp contrast, a stretched planar geometry of Ti <subscript>2</subscript> C <subscript>2</subscript> is observed in Ti <subscript>2</subscript> C <subscript>2</subscript> @ D <subscript>3 h </subscript> (5)-C <subscript>78</subscript> , where a Ti-C <subscript>2</subscript> -Ti angle of 176.87° and a long Ti-Ti distance of 5.000 Å are presented. Consistently, theoretical calculations reveal that the cluster configuration is very sensitive to the cage shape which eventually determines the electronic structures of the hybrid EMF-molecules, thus adding new insights into modern coordination chemistry.
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 59
- Issue :
- 13
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 32551612
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.0c01304