Modl, Moritz and Heinl, Sebastian and Balazs, Gabor and Calvo, Fuencisla Delgado and Caporali, Maria and Manca, Gabriele and Keilwerth, Martin and Meyer, Karsten and Peruzzini, Maurizio and Scheer, Manfred (2019) Metal-Assisted Opening of Intact P-4 Tetrahedra. CHEMISTRY-A EUROPEAN JOURNAL, 25 (25). pp. 6300-6305. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
The reactivity of ruthenium and manganese complexes bearing intact white phosphorus in the coordination sphere was investigated towards the low-valent transition-metal species [Cp ''' o] (Cp '''=eta(5)-C5H2-1,2,4-tBu(3)) and [(LM)-M-0] (L-0 = CH[CHN(2,6-Me2C6H3)] 2; M= Fe, Co). Remarkably, and irrespective of the metal species, the reaction proceeds by the selective cleavage of two P-P edges and the formation of a square-planar cyclo-P-4 ligand. The reaction products [{CpRu(PPh3)(2)}{CoCp '''}(mu,eta(1:4)-P-4)][CF3SO3] (5), [{(CpMn)-Mn-BIG(CO)(2)}(2){CoCp '''}(mu,eta(1:1:4)-P-4)] (6) and [{(CpMn)-Mn-BIG(CO)(2)}(2){ML0}(mu,eta P-1:1:4-(4))] (Cp-BIG = C-5(C(6)H(4)nBu)(5); L-0 = CH[CHN(2,6-Me2C6H3)](2); M = Fe (7a), Co (7b)), respectively, were fully characterized by single-crystal X-ray diffraction and spectroscopic methods. The electronic structure of the cyclo-P-4 ligand in the complexes 5-7 is best described as a pi-delocalized P-4(2-) system, which is further stabilized by two and three metal moieties, respectively. DFT calculations envisaged a potential intermediate in the reaction to form 5, in which a quasi-butterfly-shaped P-4 moiety bridges the two metals and behaves as an eta(3)-coordinated ligand towards the cobalt center.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | WHITE PHOSPHORUS; TETRAPHOSPHORUS COMPLEXES; ACTIVATION; LIGAND; ELEMENTS; TETRAPHOSPHACYCLOBUTADIENE; STABILIZATION; COORDINATION; HYDROLYSIS; REACTIVITY; cobalt; cyclo-P-4 ligands; diketiminate complexes; iron; phosphorus |
| 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: | 15 Apr 2020 05:53 |
| Last Modified: | 15 Apr 2020 05:53 |
| URI: | https://pred.uni-regensburg.de/id/eprint/27031 |
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