Gruenbauer, Rebecca and Schwarzmaier, Christoph and Eberl, Miriam and Balazs, Gabor and Scheer, Manfred (2021) The reactivity of the P-4-butterfly ligand [{Cp ''' Fe(CO)(2)}(2)(mu,eta(1:1)-P-4)] towards transition metal complexes: Coordination versus rearrangement. INORGANICA CHIMICA ACTA, 518: 120234. ISSN 0020-1693, 1873-3255
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The reaction of the P-4 butterfly compound [{Cp'''Fe(CO)(2)}(2)(mu,eta(1:1)-P-4)] (1, Cp''' = (C5H2Bu3)-Bu-t) towards various transition metal complexes is investigated. On the one hand, the reaction of 1 with [(PPh3)Au(tht)][PF6] (tht = tetrahydrothiophene) and [M(CO)(4)(nbd)] (M = Cr, Mo, W; nbd = norbornadiene) yields chelating complexes of the type [{Cp'''Fe(CO)(2)}(2)(mu(3),(1:1:1:1)(eta)-P-4){Au(PPh3)}] (2d) and [{Cp'''Fe(CO)(2)}(2)(mu(3),(1:1:1:1)(eta)-P-4){M(CO)(4)}] (2a-c, M = Cr, Mo, W), respectively, bearing intact P-4 butterfly ligands with exceedingly small bite angles (ca. 65 degrees). The reaction of 1 with Ag[PF6] even afforded the spiro complex [{(Cp'''Fe(CO)(2))(2)(mu(3),(1:1:1:1)(eta)-P-4)}(2)Ag][PF6] (3), in which the silver cation is coordinated in a distorted tetrahedral fashion by two P-4 butterfly motifs. On the other hand, the reaction of 1 with the carbonyl containing Lewis acids Fe-2(CO)(9) or Co-2(CO)(8) leads to rearrangement yielding [{Cp'''Fe(CO)(2)}(2){Co(CO)(3)}(2)(mu(4),(2:2:1:1)(eta)-P-4)] (4), incorporating a folded cyclo-P-4 scaffold, and [{Cp'''Fe (CO)(2)}(2)(mu(4),(1:1:1:3)(eta)-P4CO){Fe(CO)(4)}{Fe(CO)(3)}] (5), displaying a tetraphosphole structural motif obtained after carbonyl insertion, respectively. The products are comprehensively characterized by different spectroscopic methods as well as single crystal X-ray diffraction analysis and theoretical calculations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | P-4 ACTIVATION; CRYSTAL-STRUCTURE; NMR-SPECTROSCOPY; DYNAMIC-BEHAVIOR; FACILE SYNTHESIS; BUILDING-BLOCKS; PENTAPHOSPHAFERROCENE; CHEMISTRY; CP2MO2(CO)(4)(ETA(2)-P-2); POLYPHOSPHORUS; P-4-butterfly; cyclo-P-4 ligands; Polyphosphorus ligands; Carbonyl complexes; P-31 NMR; DFT calculations |
| 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: | 07 Jul 2022 06:58 |
| Last Modified: | 07 Jul 2022 06:58 |
| URI: | https://pred.uni-regensburg.de/id/eprint/45859 |
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