Ordyszewska, Anna and Szynkiewicz, Natalia and Ponikiewski, Lukasz and Scheer, Manfred and Pikies, Jerzy and Grubba, Rafal (2019) Syntheses and Structures of Transition Metal Complexes with Phosphanylphosphinidene Chalcogenide Ligands. INORGANIC CHEMISTRY, 58 (12). pp. 7905-7914. ISSN 0020-1669, 1520-510X
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The reactivity of the phosphanylphosphinidene complex [(DippN)(2)W(Cl)(eta(2)-P-PtBu2)](-) (1) toward chalcogens (Ch = Se, S) was studied. Reactions of stoichiometric amounts of 1 with chalcogens in DME yielded monomeric tungsten complexes with phosphanylphosphinidene chalcogenide ligands of the formula tBu(2)P-P-Ch (Ch = Se (in 2) and S (in 5)), which can be regarded as products of the addition of a chalcogen atom to a P=W bond in starting complex 1. The dissolution of selenophosphinidene complex 2 in nondonor solvents led to the formation of a dinuclear complex of tungsten (3) bearing a tBu(2)P(Se)-P ligand together with [tBuSe(2)Li(dme)(2)](2) and polyphosphorus species. Under the same reaction conditions, thiophosphinidene complex 5 dimerized via the formation of transient complex 7, possessing a thiotetraphosphane-diido moiety tBu(2)P(S)-P-P-PtBu2. The elimination of the tBu(2)PS group from 7 yielded stable dinuclear tungsten complex 8 with an unusual phosphinidene tBu(2)P-P-P ligand. The reaction of 1 with excess chalcogen led to the cleavage of the P-P bond in the tBu(2)P-P ligand and the formation of [(DippN)(2)W(PCh(4))](2)(2-) and [tBuCh(2)Li(dme)(2)](2). The isolated compounds were characterized by NMR spectroscopy and X-ray crystallography. Furthermore, the calculated geometries of the free selenophosphinidenes, tBu(2)P-P-Se and tBu(2)P(Se)-P, were compared with their geometries when serving as ligands in complexes 2 and 3.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CARBENE-LIKE CHEMISTRY; BOND COVALENT RADII; PHOSPHINIDENE COMPLEXES; PHOSPHINOPHOSPHINIDENE (BU2P)-BU-T-P; PHOSPHORUS ANALOGS; TRAPPING REACTION; REACTIVITY; OXIDE; COORDINATION; TUNGSTEN(VI); |
| 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: | 08 Apr 2020 08:07 |
| Last Modified: | 08 Apr 2020 08:07 |
| URI: | https://pred.uni-regensburg.de/id/eprint/26829 |
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