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First-Row Transition-Metal Complexes of the 1-Methoxycyclobutenedionate(1−) Ion

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journal contribution
posted on 09.08.1999, 00:00 by Hazel-Ann Hosein, Hema Jaggernauth, Bert D. Alleyne, Lincoln A. Hall, Andrew J. P. White, David J. Williams
The synthesis and characterization by single-crystal X-ray crystallography of a series of monomeric first-row transition-metal complexes with the 1-methoxycyclobutenedionate(1−) ligand are described. The isomorphous compounds [M(CH3OC4O3)2(H2O)4] (M = Mn, Co, Ni, Zn) are C2 symmetric and crystallize in the monoclinic space group C2/c. The metal atom in each of these complexes is six-coordinate with two cis 1-methoxycyclobutenedionate(1−) ligands, the methoxy substituent being oriented cis with respect to the ligating oxygen atom. The remaining coordination sites are filled by four aqua ligands. Monomers are linked by O−H···O hydrogen bonds to form arrays of stepped tapes. Hydrolysis of the methoxy group on the ligand occurs during the formation of the copper complex and {[Cu(C4O4)(H2O)2]·0.25H2O}n is produced. This complex crystallizes in the tetragonal space group P4/n and has a structure similar to, but differing significantly from, those of a series of 3-dimensional cage squarates which have been reported previously.