Trabitsch, Karolina and Hauer, Sebastian and Schwedtmann, Kai and Royla, Philipp and Weigand, Jan J. and Wolf, Robert (2025) Phosphorus ring expansion at cobalt: targeted synthesis of P4, P5, and P7 ligands. INORGANIC CHEMISTRY FRONTIERS, 12 (5). pp. 2013-2023. ISSN 2052-1553
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We report the synthesis of extended polyphosphorus ligands through the condensation of CoP3 and CoP4 frameworks with P1 and P2 units. Tetraphosphido complexes [(L)Co(CN)(eta 3-P4R2)] (1a-R: L = PHDI; R = Cy, Ph; 1b-R: L = Ar*BIAN; R = Cy, N(iPr)2) were obtained by treatment of the anionic cyclo-P3 complexes [nBu4N][(PHDI)Co(CN)(eta 3-P3)] (H, PHDI = bis(2,6-diisopropylphenyl)phenanthrene-9,10-diimine) and [K(18c-6)][(Ar*BIAN)Co(CN)(eta 3-P3)] (I, BIAN = 1,2-bis(arylimino)acenaphthene diimine with aryl being 2,6-dibenzhydryl-4-isopropylphenyl) with diorganochlorophosphanes (R2PCl, R = Cy, Ph, or N(iPr)2). Similar reactions of the cyclo-P4 complex [K(18c-6)][(Ar*BIAN)Co(eta 4-P4)] (K) yielded pentaphosphido complexes [K(18c-6)][(Ar*BIAN)Co(eta 4-P5R2)] (2b-R; R = tBu, N(iPr)2). Importantly, we show that the previously reported cationic cyclo-tetraphosphane [(LC)4P4][OTf]4 (G[OTf]4, LC = 4,5-dimethyl-1,3-diisopropylimidazol-2-yl) can be used to introduce [LC-P]+ and [LC-P]22+ units. Depending on the stoichiometry and reaction conditions, the reaction of G[OTf]4 with complex H furnishes complexes [(PHDI)Co(CN)(eta 3-P4LC)] (3a) and [(PHDI)Co(CN)(eta 3-P5(LC)2)][OTf] (4a[OTf]) with eta 3-coordinated tetra- and pentaphosphido ligands. Expanding this strategy, the cyclo-P5 and cyclo-P7 complexes [(PHDI)Co(mu:eta 4,eta 1-P5LC){W(CO)5}] (5a-W(CO)5) and [(PHDI)Co(mu 3:eta 2:eta 2,eta 1,eta 1-P7LC){W(CO)5}2] (6a-{W(CO)5}2) were isolated from the reaction of G[OTf]4 with [K(18c-6)][(PHDI)Co(eta 4-P4)] (J) upon addition of W(CO)5(THF) to the reaction mixture. Intermediates en route to products 5a and 6a were detected by 31P{1H} NMR spectroscopy. The Ar*BIAN complexes I and K afford structurally analogous compounds 3b to 6b. Compounds 3-6 were isolated as crystalline materials and characterized by single-crystal X-ray diffraction and multinuclear NMR spectroscopy.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | BOND COVALENT RADII; P-P BOND; ACTIVATION; COMPLEXES; INSERTION; ELEMENTS; FUNCTIONALIZATION; FRAGMENTATION; TETRAHEDRON; SILYLENE |
| 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: | 17 Jun 2026 04:48 |
| Last Modified: | 17 Jun 2026 04:48 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66479 |
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