Synthesis and Structure of Diphosphene-Bridged Dicarborane Dianions with [2 <i>n</i> +3] Skeletal Electrons
In contrast to the extensively studied carboranes with even skeletal electron counts ([2<i>n</i>+2], [2<i>n</i>+4]), systems with odd electron counts ([2<i>n</i>+3]) are rare (<i>n</i> = number of skeletal atoms). With the assistance of a diphosphene-bridge, dicarborane dianions {[(Ar)NC(<sup>t</sup>Bu)C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>]P}<sub>2</sub><sup>2-</sup> [Ar = Dipp (<b>2</b>) or Dmp (<b>4</b>); Dipp = 2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>, Dmp = 2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>] with formal [2<i>n</i>+3] skeletal electrons in each carborane cage were obtained via single electron reduction of imine-stabilized carboranyl-phosphinidene or -diphosphene with potassium graphite (KC<sub>8</sub>) or cobaltocene (CoCp<sub>2</sub>), respectively. The delocalization of the two unpaired electrons across the carborane cages and diphosphene-bridge was evidenced by experimental and theoretical results.
Authors
- Tek Long Chan (ORCID: https://orcid.org/0000-0002-0391-5746)
- Jie Zhang (ORCID: https://orcid.org/0000-0002-6509-8614)
- Zuowei Xie
Institutions
- Chinese University of Hong Kong (HK)
- Southern University of Science and Technology (CN)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-12-22
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c04262
- Primary Topic
- Boron Compounds in Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00