Deng, Shining and Schwarzmaier, Christoph and Zabel, Manfred and Nixon, John F. and Bodensteiner, Michael and Peresypkina, Eugenia V. and Balazs, Gabor and Scheer, Manfred (2011) Remarkable Differences in the Coordination Chemistry of Structurally Related 1,2,4-Triphosphaferrocenes with Copper(I) Halides and Silver(I) Salts. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (19). pp. 2991-3001. ISSN 1434-1948, 1099-0682
Full text not available from this repository. (Request a copy)Abstract
The coordination behavior of 1,2,4-triphosphaferrocenes [FeCpR(eta(5)-P(3)C(2)tBu(2))] [Cp-R = Cp (1), Cp''' = eta(5)-C(5)H(2)tBu(3) (3)] towards Cu-I halides is significantly influenced by the substitution pattern of the cyclopentadienyl ring attached to the iron atom. The reaction of the Cp derivative 1 with CuBr in a 1:1 stoichiometry leads to the dimeric complex [{FeCp(eta(5):eta(1):eta(1)-P(3)C(2)tBu(2))}{mu-CuBr(MeCN)}](2) (5b), in which two 1,2,4-triphosphaferrocenes are linked by two CuBr units. By using a 1:2 stoichiometry, the 1D polymeric compound [{FeCp(eta(5):eta(1):eta(1):eta(1)-P(3)C(2)tBu(2))}mu-{(CuBr)(3)(MeCN)(2)}](n) (6) is formed in which the triphosphaferrocenes are bridged by (CuBr) 2{CuBr(MeCN) 2} units. Starting from CuI, independent of the stoichiometry, the cage compound [{FeCp(eta(5):eta(1):eta(1)-P(3)C(2)tBu(2))}(3){Cu(mu-I)}(3){Cu(mu(3)-I)}(3){Cu(NCMe)}(mu(6)-I)] (7) is formed. However, if the bulky Cp''' derivative 3 is used already in a 1:1 stoichiometry with CuBr, a transformation of the initially five-membered 1,2,4-triphospholyl ring into a four-membered 1,2-diphosphete ligand is observed, which is linked by CuBr moieties forming the dimeric paramagnetic complex [{FeCp'''(eta(4):eta(1):eta(1)-P(2)C(2)tBu(2))}(mu-CuBr)](2) (9). Furthermore, applying a 1:2 stoichiometry between 3 and CuX (X = Br, I) the complete fragmentation of the 1,2,4-triphospholyl ring under mild conditions into a tetraphosphabutadiene ligand is observed. In the formed 1D polymeric complexes [{(FeCp''') 2(mu,eta(4):eta(1):eta(1)-P-4)}{(mu-CuX)(2)(MeCN)}] n [X = Br (10a), I (10b)] this ligand represents now the middle deck of the triple-decker sandwich complexes linked by four-membered [(CuX)(2)(CH3CN)] moieties. Moreover, the reaction of the Cp derivative 1 with the Ag salt of the weakly coordinating anion [Al{OC(CF3)(3)}](4)(-) leads to the dimeric Ag(CH3CN)-bridged dicationic product [{FeCp(eta(5)-P(3)C(2)tBu(2))} Ag-(MeCN)](2)[Al{OC(CF3)(3)}(4)](2) (11).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | LIGAND COMPLEXES; IRON COMPLEXES; PENTAPHOSPHAFERROCENE; BEHAVIOR; REFINEMENT; FRAMEWORKS; POLYMERS; DESIGN; Supramolecular chemistry; Coordination polymers; Copper; Fragmentation reactions; Silver; Tetraphosphabutadiene ligand |
| 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 Jun 2020 10:29 |
| Last Modified: | 08 Jun 2020 10:29 |
| URI: | https://pred.uni-regensburg.de/id/eprint/20579 |
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