Synthesis, Properties, and Structural Characterization of Novel d5, d6, and d7 Transition-Metal Complexes with Cyclic Diphosphonium Triple-Ylide Anions

H. Schmidbaur, T. Costa, B. Milewski-Mahrla, F. H. Köhler, Y. H. Tsay, C. Krüger, J. Abart, F. E. Wagner, Y. H. Tsay, C. Krüger, J. Abart, F. E. Wagner

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20 Scopus citations

Abstract

Reaction of the lithiated cyclic double-ylide Li+L (2) with the tetrahydrofuran adducts of MnBr2, FeCl2, and CoCl2 at −78 °C in tetrahydrofuran results in the formation of the novel binary metal ylide complexes MnL2 (3), FeL2 (4), and CoL2 (5), where L represents the cylic triple-ylide anion corresponding to the neutral ylide 1 (LH). The deeply colored, air-sensitive compounds crystallize with 2 mol of crystal THF, which can be removed in vacuo. All three complexes are strongly paramagnetic and exhibit Curie-Weiss behavior in susceptibility measurements between 4.2 and 298.5 K. The magnetic moments correspond to a normal high-spin configuration of d5, d6, and d7 metal ions in a tetrahedral environment. The results of a 57Fe Mössbauer investigation of 4 at 4.2 K are also in good agreement with the tetrahedrally coordinated high-spin iron(II) model. The signals in the paramagnetic 1H NMR spectrum of the iron complex 4 in tetrahydrofuran can be assigned on the basis of the proposed structure and are found to follow Curie's law in the temperature range between ca. 300 and 360 K. The single-crystal X-ray diffraction study of the manganese complex 3 established the proposed structure (a = 2848.5 (5) pm, b = 1298.0 (2) pm, c = 1968.9 (2) pm, β = 110.51 (1)°, space group C2/c, Z = 4). The manganese cation is surrounded by two symmetry-related, equivalent triple-ylide anions. The seven-membered ylide heterocycles are folded in a boat conformation and have metal-ligand contacts mainly through the benzylide carbon atoms, which form a distorted tetrahedral array around the Mn(II) center. Metal-phenylene interactions are not fully excluded, however, as judged by the Mn-C distance pattern. The crystals of the Co(II) analogue 5 are isomorphous with the crystals of 3.

Original languageEnglish
Pages (from-to)1266-1270
Number of pages5
JournalOrganometallics
Volume1
Issue number10
DOIs
StatePublished - 1982
Externally publishedYes

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