Hauer, Sebastian and Balazs, Gabor and Gliese, Fabian and Meurer, Florian and Downie, Thomas M. Horsley and Hennig, Christoph and Weigand, Jan J. and Wolf, Robert (2024) Functionalization of Tetraphosphido Ligands by Heterocumulenes. INORGANIC CHEMISTRY, 63 (43). pp. 20141-20152. ISSN 0020-1669, 1520-510X
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Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P-4), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P-4 ligands. Specifically, the reaction of carbon disulfide (CS2) with [K(18c-6)][(Ar*BIAN)Co(eta(4)-P-4)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(eta(3):eta(1)-P4CS2)] ([K(18c-6)]3), in which CS2 is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe3)(2) into a P-P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(eta(3):eta(1)-P4SN2(SiMe3)(2))] (K(18c-6)]4). This salt further reacts with Me3SiCl to form [(Ar*BIAN)Co(eta(3):eta(1)-P4SN2(SiMe3)(3)] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(eta(3):eta(1)-P4C(O)tBu)] (2) with isothiocyanates results in P-C bond insertion, yielding [(Ar*BIAN)Co(eta(3):eta(1)-P4C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MULTINUCLEAR MAGNETIC-RESONANCE; BOND COVALENT RADII; P-4 ACTIVATION; BASIS-SETS; COORDINATION CHEMISTRY; BUTTERFLY COMPLEXES; WHITE PHOSPHORUS; METAL; REACTIVITY; MOLECULES; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 03 Sep 2025 11:27 |
| Last Modified: | 03 Sep 2025 11:27 |
| URI: | https://pred.uni-regensburg.de/id/eprint/64288 |
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