T. Ohishi, K. Kashiwabara, J. Fujita
Feb 1, 1986
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0
Influential Citations
19
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Journal
Bulletin of the Chemical Society of Japan
Abstract
Monomeric (yellow) and dimeric (red) cobalt(III)–dioxygen complexes containing 1,2-bis(dimethylphosphino)ethane (dmpe) have been prepared from [Co(dmpe)2]+ and [Co(dmpe)2]2+, respectively, by air oxidation. The 1,3-bis(dimethylphosphino)propane (dmpp) complex afforded only the monomeric dioxygen complex by either preparative method. The crystal structures of [Co(O2)(dmpe)2]B(C6H5)4 (1) and [Co(O2)(dmpp)2]BF4·H2O (2) have been determined by X-ray analysis. Crystal data for 1; monoclinic, P21⁄a, a=18.011(12), b=18.761(10), c=11.455(6) A, β=107.78(4)°, V=3686(4) A3, Z=4, and R=0.064. Crystal data for 2; orthorhombic, Pbcn, a=14.540(5), b=13.123(4), c=13.138(2) A, V=2507(1) A3, Z=4, and R=0.076. The complex ions in both 1 and 2 have a trigonal-bipyramidal coordination geometry when the O2 group bonded to the Co atom in the side-on form at a coordination site of the trigonal plane is assumed to be a unidentate ligand. Bond lengths. Co–O (1.858(7)–1.881(4) A) and O–O (1.414(12) and 1.425(6) A), and O–O stretchi...