Scheer, Manfred and Gregoriades, Laurence J. and Zabel, Manfred and Bai, Junfeng and Krossing, Ingo and Brunklaus, Gunther and Eckert, Hellmut (2008) Self-assemblies based on [CP2Mo2(CO)(4)(mu,eta(2)-P-2)]-solid-state structure and dynamic behaviour in solution. CHEMISTRY-A EUROPEAN JOURNAL, 14 (1). pp. 282-295. ISSN 0947-6539,
Full text not available from this repository. (Request a copy)Abstract
Reaction of complex [CP2Mo2(CO)(4)(mu,eta(2)-P-2)] (Cp = C5H5 (1)) with CuPF6, AgX (X = BF4, ClO4, PF6, SbF6, Al{OC(CF3)(3)}(4)) and [(Ph3P)Au(THF)][PF6] (THF = tetrahydrofuran), respectively, results in the facile formation of the dimers 3b-h of the general formula [M-2({Cp2Mo2 (CO)(4) (mu,eta(2):eta(2)-P-2)}(2))([Cp2Mo2(CO)(4) (mu,eta(2):eta(1):eta(1)-P-2)}(2))][X](2) (M = Cu, Ag, Au; X = BF4, ClO4, PF6, SbF6, Al{OC(CF3)(3)}(4)). As revealed by X-ray crystallography, all these dimers comprise dicationic moieties that are well-separated from the weakly coordinating anions in the solid state. If 1 is allowed to react with AgNO2 and LAuCl (L = CO or tetrahydrothiophene), respectively, the dimer [Ag-2{Cp2Mo2(CO)(4) (mu,eta(2):eta(1):eta(1)-P-2)}(2)(eta(2)-NO2)(2)] (5) and the complex [AuCl{Cp2Mo2(CO)(4)(mu,eta(2):eta(1)-P-2)}] (6) are formed, which have also been characterised by X-ray crystallography. In compounds 5 and 6, the anions remain coordinated to the Group 11 metal centres. Spectroscopic data suggest that the dimers 3b-h display dynamic behaviour in solution and this is discussed by using the comprehensive results obtained for 3g (M = Ag; X = Al{OC(CF3)(3)}(4)) as a basis. The interpretation of the experimental results is facilitated by density functional theory (DFT) calculations on 3g (structures, energetics, NMR shielding tensors). The P-31 magic angle spinning (MAS) NMR spectra recorded for the dimers 3b (M = Cu; X = PF6) and 3c (M = Ag; X = BF,) as well as that of the previously reported one-dimensional (1D) polymer [Ag-2{Cp2Mo2(CO)(4)( mu,eta(2):eta(1):eta(1)-P-2)}(3)(mu,eta(2):eta(1)-NO3)](n)[NO3](n) (4) are also discussed herein and the strong dependence of the chemical shift of the phosphorus atoms within each compound on subtle structural differences in the solid state is demonstrated. Furthermore, the X-ray crystallographic and P-31 MAS NMR spectroscopic characterisation of a new polymorph of 1 is reported.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | WEAKLY COORDINATING ANIONS; CRYSTAL-STRUCTURE DETERMINATIONS; ONE-DIMENSIONAL POLYMERS; GAUSSIAN-BASIS SETS; MOLECULAR-STRUCTURE; METAL(I) COMPOUNDS; NMR-SPECTROSCOPY; ATOMS LI; COMPLEXES; ADDUCTS; density functional calculations; group 11 metals; molybdenum; NMR spectroscopy; 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: | 11 Nov 2020 13:31 |
| Last Modified: | 11 Nov 2020 13:31 |
| URI: | https://pred.uni-regensburg.de/id/eprint/31578 |
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