Dimeric “paddle-wheel” cymantrenylcarboxylates of copper (II)

• Published in: Inorganica Chimica Acta Vol. 384; pp. 18 - 22
• Main Authors: Pasynskii, A.A., Shapovalov, S.S., Gordienko, A.V., Razuvaev, D.I., Skabitsky, I.V., Aleksandrov, G.G., Dobrohotova, Zh.W., Bogomyakov, A.S.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.04.2012
• Subjects: Copper; Cyclopentadienyl complexes; Manganese; Transition metal; Transition metal; Copper; Cyclopentadienyl complexes; Manganese
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2011.11.026

Four novel LCu(CymCOO)4CuL complexes where Cym=η5-C5H4Mn(CO)3, L= THF (I), Et2O(II), CymCOOH (III) or PPh3 (IV) have been synthesized. The structures of I–III were solved by X-ray analyses. The thermodestruction of I and II leads to complete decarboxylation, then to elimination of nine CO groups from 12 and finally to loosing of all cyclopentadienyl groups with metal Cu and Mn1.5Cu1.5O4 formation. [Display omitted] ► Cu (II) complexes with cymantrenylcarboxylate ligands were synthesized. ► The structures of two complexes were elucidated by X-ray diffraction. ► Thermal decay of Cu (II) cymantrenylcarboxylates under air results in Cu1.5Mn1.5O4 and metallic Cu. The interaction of cymantrenylcarboxylic acid (C5H4CO2H)Mn(CO)3 (CymCOOH) or its potassium salts with salts of Cu (II) in alcohol or water with subsequent treatment with ligands L gives binuclear complexes LCu(CymCOO)4CuL where L=THF (I), Et2O (II), CymCOOH (III) or PPh3 (IV). The structures of I–III were solved by X-ray analyses. The frame of all complexes is constructed as “paddle-wheel” with four carboxylate bridges. At thermal decomposition of I and II in Ar the loss of L ligands took place, then the decarboxylation of all CymCOO groups was observed followed by decarbonylation with elimination of nine CO groups only. Finally the loss of cyclopentadienyl ligands results the solid product which according to powder XRD data contains metallic copper and Mn1.5Cu1.5O4 phase probably due to the splitting of the retaining CO groups.