Kelly, John A. and Streitferdt, Verena and Dimitrova, Maria and Westermair, Franz F. and Gschwind, Ruth M. and Berger, Raphael J. F. and Wolf, Robert (2022) Transition-Metal-Stabilized Heavy Tetraphospholide Anions. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 144 (44). pp. 20434-20441. ISSN 0002-7863, 1520-5126
Full text not available from this repository. (Request a copy)Abstract
Phosphorus analogues of the ubiquitous cyclopenta-dienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heavier group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopentadienyl anions SnP42-and PbP42-. The complexes [(q4-tBu2C2P2)2Co2(mu,q5:q5- P4Tt)] [Tt = Sn (6), Pb (7)] are formed by reaction of white phosphorus (P4) with cyclooctadiene cobalt complexes [Ar ' TtCo(q4- P2C2tBu2)(q4-COD)] [Tt = Sn (2), Pb (3), Ar ' = C6H3-2,6{C6H3- 2,6-iPr2}2, COD = cycloocta-1,5-diene] and Tt{Co(q4-P2C2tBu2)-(COD)}2 [Tt = Sn (4), Pb (5)]. While the SnP42- complex 6 was isolated as a pure and stable compound, compound 7 eliminated Pb(0) below room temperature to afford [(q4- tBu2C2P2)2Co2(mu,q4:q4-P4) (8), which is a rare example of a tripledecker complex with a P42- middle deck. The electronic structures of 6-8 are analyzed using theoretical methods including an analysis of intrinsic bond orbitals and magnetic response theory. Thereby, the aromatic nature of P5- and SnP42- was confirmed, while for P42-, a specific type of symmetry-induced weak paramagnetism was found that is distinct from conventional antiaromatic species.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | COORDINATION CHEMISTRY; MOLECULAR-STRUCTURE; GROUP-14 METALLOLES; ORGANIC-CHEMISTRY; COBALT COMPLEXES; X-RAY; CRYSTAL; PHOSPHORUS; OXIDE; DIMERIZATION; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 05 Feb 2024 15:17 |
| Last Modified: | 05 Feb 2024 15:17 |
| URI: | https://pred.uni-regensburg.de/id/eprint/57312 |
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