Taube, Clemens and Schwedtmann, Kai and Noikham, Medena and Somsook, Ekasith and Hennersdorf, Felix and Wolf, Robert and Weigand, Jan J. (2020) P-P Condensation and P-N/P-P Bond Metathesis: Facile Synthesis of Cationic Tri- and Tetraphosphanes. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 59 (9). pp. 3585-3591. ISSN 1433-7851, 1521-3773
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[LC (R) P((PhP)(2)C2H4)][OTf] (4 a,b[OTf]) and [(LCP)-P-iPr(PPh2)(2)][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl-substituted dipyrazolylphosphane triflate salts [LC (R) P(pyr)(2)][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; L-C (R)=1,3-dialkyl-4,5-dimethylimidazol-2-yl; pyr=3,5-dimethylpyrazol-1-yl) with the secondary phosphanes PhP(H)C2H4P(H)Ph) and Ph2PH. A stepwise double P-N/P-P bond metathesis to catena-tetraphosphane-2,3-diium triflate salt [(Ph2P)(2)((LCP)-P-Me)(2)][OTf](2) (7 a[OTf](2)) is observed when reacting 3 a[OTf] with diphosphane P2Ph4. The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH3CN)(4)]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2PPLCiPr)Au}(4)][OTf](4) (9[OTf](4)) was unexpectedly formed as a result of a chloride-induced P-P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH3CN)(3)][OTf](2) (M=Cu, Ag) (10[OTf](2), 11[OTf](2)).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOSPHORUS; CHEMISTRY; CHAIN; TRIPHOSPHANES; COMPLEXES; BEHAVIOR; PHOSPHINES; R=CH3; C2H5; cationic polyphosphanes; gold complex; phosphorus ligands; P-P bond metathesis; reductive coupling |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 19 Mar 2020 09:12 |
| Last Modified: | 19 Mar 2020 09:12 |
| URI: | https://pred.uni-regensburg.de/id/eprint/25648 |
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