Gregoriades, Laurence J. and Wegley, Brian K. and Sierka, Marek and Brunner, Eike and Groeger, Christian and Peresypkina, Eugenia V. and Virovets, Alexander V. and Zabel, Manfred and Scheer, Manfred (2009) One-Dimensional Polymers Based on Silver(I) Cations and Organometallic cyclo-P-3 Ligand Complexes. CHEMISTRY-AN ASIAN JOURNAL, 4 (10). pp. 1578-1587. ISSN 1861-4728, 1861-471X
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The synthesis and characterization of the first supramolecular aggregates incorporating the organometallic cyclo-P-3 ligand complexes [(CpMo)-Mo-R(CO)(2)(eta(3)-P-3)] (Cp-R=Cp (C5H5; 1a), Cp* (C-5(CH3)(5); 1b)) as linking units is described. The reaction of the Cp derivative la with AgX (X= CF3SO3, Al(OC(CF3)(3))(4)) yields the one-dimensional (1D) coordination polymers [Ag(CpMo(CO)(2)(mu,eta(3):eta(1):eta(1)-P-3)](2)]n[Al{OC(CF3)(3)}(4)]n (2) and [Ag-CPMo(CO)(2)(mu,eta(3):eta(1):eta(1)-P-3)}(3)](n)[X](n) (X= CF3SO3 (3a), Al{OC(CF3)(3)}(4) (3b)). The solid-state structures of these polymers were revealed by X-ray crystallography and shown to comprise polycationic chains well-separated from the weakly coordinating anions. If AgCF3SO3 is used, polymer 3a is obtained regardless of reactant stoichiometry whereas in the case of Ag[Al{OC(CF3)(3)}(4)], reac-tant stoichiometry plays a decisive role in determining the structure and composition of the resulting product. Moreover, polymers 3a, b are the first examples of homoleptic silver complexes in which Ag-I centers are found octahedrally coordinated to six phosphorus atoms. The Cp* derivative 1b reacts with Ag[Al(OC(CF3)(3)}(4)] to yield the 1D polymer [Ag(Cp*Mo(CO)(2)(mu,eta(3):eta(2):eta(1)-P-3)}(2)](n)[Al{OC- (CF3)(3)}(4)](n) (4), the crystal structure of which differs from that of polymer 2 in the coordination mode of the cyclo-P-3 ligands: in 2, the Ag+ cations are bridged by the cyclo-P-3 ligands in a eta(1):eta(1) (edge bridging) fashion whereas in 4, they are bridged exclusively in a eta(2):eta(1) mode (face bridging). Thus, one third of the phosphorus atoms in 2 are not coordinated to silver while in 4. all phosphorus atoms are engaged in coordination with silver. Comprehensive spectroscopic and analytical measurements revealed that the polymers 2, 3a,b, and 4 depolymerize extensively upon dissolution and display dynamic behavior in solution, as evidenced in particular by variable temperature P-31 NMR spectroscopy. Solid-state P-31 magic angle spinning (MAS) NMR measurements, performed on the polymers 2, 3b, and 4. demonstrated that the polymers 2 and 3b also display dynamic behavior in the solid state at room temperature. The X-ray crystallographic characterisation of 1b is also reported.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CROWN THIOETHER CHEMISTRY; TOTAL-ENERGY CALCULATIONS; RAY CRYSTAL-STRUCTURE; AUGMENTED-WAVE METHOD; COORDINATION CHEMISTRY; NMR-SPECTROSCOPY; REDOX PROPERTIES; BASIS-SETS; APPROXIMATION; PENTAPHOSPHAFERROCENE; density functional calculations; molybdenum; phosphorus; silver; supramolecular chemistry |
| Subjects: | 500 Science > 540 Chemistry & allied sciences 500 Science > 570 Life sciences |
| Divisions: | Biology, Preclinical Medicine > Institut für Biophysik und physikalische Biochemie > Alumni or Retired > Prof. Dr. Eike Brunner Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Oct 2020 06:15 |
| Last Modified: | 12 Oct 2020 06:15 |
| URI: | https://pred.uni-regensburg.de/id/eprint/29675 |
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