Rummel, Eva-Maria and Elsayed Moussa, Mehdi and Parzefall, Maria and Peresypkina, E. and Riesinger, Christoph and Timoshkin, A. Y. and Balazs, Gabor and Mastrorilli, P. and Todisco, S. and Scheer, Manfred (2025) Synthesis, oxidation and unusual coordination chemistry of the diphosphete complex [(Cp′′′Co)2(μ,η<SUP>4:4</SUP>-(CH3CP)2)]. INORGANIC CHEMISTRY FRONTIERS, 12 (3). pp. 967-974. ISSN 2052-1553,
Full text not available from this repository. (Request a copy)Abstract
Notwithstanding four decades of active research, very rare examples of diphosphabutadiene complexes arising from dimerisation of the phosphaalkyne CH3-C 00000000000000000 00000000000000000 00000000000000000 01111111111111110 00000000000000000 01111111111111110 00000000000000000 01111111111111110 00000000000000000 00000000000000000 00000000000000000 P have been reported. Herein, we show that methyl phosphaalkyne dimerises in the coordination sphere of Cp ''' Co fragments to yield the unprecedented diphosphete complex [Cp ''' Co(eta 4-P2C2Me2)] (1) and the triple-decker complex [{Cp ''' Co}2(mu,eta 4:eta 4-P2C2Me2)] (2). Compound 2 can be oxidised with Ag[Al{OC(CF3)3}4] (Ag[TEF]) to give [{Cp ''' Co}2(mu,eta 4:eta 4-P2C2Me2)][TEF] (3). Additionally, it shows an unusual coordination behaviour towards copper halides and [W(CO)4(nbd)] (nbd = norbornadiene). Its reaction with CuCl leads to the formation of the 1D polymer [{Cp ''' Co}2(mu,eta 4:eta 2:eta 1:eta 1-P2C2Me2){Cu(mu-Cl)}2]n (6) while its reaction with CuBr, CuI and [W(CO)4(nbd)] results in the metallacyclic compounds [(Cp ''' Co){mu 3,eta 4:eta 1:eta 1-P2C2Me2}(CH3CN){Cu(mu-X)}2]2 (X = Br (7a), I (7b)) and [Cp ''' Co{mu 3,eta 4:eta 1:eta 1-P2C2Me2}{W(CO)4}]3 (8). In 6, an isomerisation of the diphosphete ring to a diphosphacyclopentadienyl ring occurs. In 7 and 8, the loss of Cp ''' Co moieties from the former compound 2 is observed. The formation of 1,3-diphosphete rings in 1 and 2 instead of the more thermodynamically favoured 1,2-diphosphete rings are explained by DFT computations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | RING EXPANSION; PHOSPHORUS; PHOSPHAALKYNES; REACTIVITY; TUNGSTEN; 1,3-DIPHOSPHACYCLOBUTADIENE; PHOSPHAETHYNE; DIMERIZATION; CRYSTAL; HCP; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 17 Mar 2026 07:16 |
| Last Modified: | 17 Mar 2026 07:16 |
| URI: | https://pred.uni-regensburg.de/id/eprint/64333 |
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