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Synthesis and Reaction Chemistry of Heterodi- and Heterotrimetallic Transition-Metal Complexes Based on 1-(Diphenylphosphanyl)-1′-terpyridylferrocene

Authors

  • Alexander Hildebrandt,

    1. Technische Universität Chemnitz, Fakultät fürNaturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany, Fax: +49-371-531-21219
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  • Nora Wetzold,

    1. Technische Universität Chemnitz, Fakultät fürNaturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany, Fax: +49-371-531-21219
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  • Petra Ecorchard,

    1. Technische Universität Chemnitz, Fakultät fürNaturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany, Fax: +49-371-531-21219
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  • Bernhard Walfort,

    1. Technische Universität Chemnitz, Fakultät fürNaturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany, Fax: +49-371-531-21219
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  • Tobias Rüffer,

    1. Technische Universität Chemnitz, Fakultät fürNaturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany, Fax: +49-371-531-21219
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  • Heinrich Lang

    1. Technische Universität Chemnitz, Fakultät fürNaturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany, Fax: +49-371-531-21219
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Abstract

The reaction of [Fe(η5-C5H4PPh2)(η5-C5H4terpy)] (5; terpy = 2,2′:6′,2″-terpyridin-4′-yl) with diverse transition-metal compounds including [PtCl2(Et2S)2], [Pd(cod)X2], [AuCl(tht)], [CuBr], [Mo(CO)4(nbd)], and [{RhCl(cod)}2] (X = Cl, Br; tht = tetrahydrothiophene; nbd = norbornadiene; cod = cyclooctadiene) to afford heterobi- and trimetallic complexes and a coordination polymer is reported. The following compounds were prepared: [Fe(η5-C5H4PPh2{PtCl2(SEt2)})(η5-C5H4terpy)] (7), trans-[PtCl2{(Ph2P-η5-C5H4)(η5-C5H4terpy)Fe}2] (9), [Fe(η5-C5H4PPh2PdCl2)(η5-C5H4terpy)] (12), [Fe{η5-C5H4PPh2(Cl3Pd)}(η5-C5H4terpy{(dmso)2ClNi+})] (14), trans-[PdX2{(Ph2P-η5-C5H4)(η5-C5H4terpy)Fe}2] (16a, X = Cl;16b, X = Br), [Mo(CO)4{(η5-C5H4PPh2)(η5-C5H4terpy)Fe}2](17), [Fe{η5-C5H4Ph2P(CuBr)}(η5-C5H4terpy)]n (19), [Fe{η5-C5H4Ph2P(AuCl)}(η5-C5H4terpy)] (22), [Fe(η5-C5H4Ph2P{Rh(cod)Cl})(η5-C5H4terpy)] (23), [Ru({η5-C5H4Ph2P(AuCl)}(η5-C5H4terpy)Fe)2]Cl2 (25), and [Fe{η5-C5H4PPh2(PdCl2)}{η5-C5H4-CH=CHC(O)(py)}] (26). The molecular structures of 5, 9, 12, 14, 16b, 22, and 26 in the solid state are reported. They show typical features of related phosphanylferrocenes and terpyridylferrocenes. Characteristic of 12 is a C–H activation as a result of the close distance of palladium to the terpyridyl moiety. Complexes 12, 26, and [PdCl2(dppf)] [dppf = 1,1′-bis(diphenylphosphanyl)ferrocene], for comparison, were used in preliminary studies as catalysts in the carbon–carbon coupling of iodobenzene with tert-butyl acrylate to give (E)-tert-butyl cinnamate. The conversion amounts to 80 % with a turnover number of 160 and turnover frequency of 48 h–1.

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