SYNTHESES, CHARACTERIZATION, AND REACTIVITY OF MANGANESE AND RHENIUM DIOXIME COMPLEXES - X-RAY CRYSTAL-STRUCTURES OF MN(II)(CDO)(CDOH)2(BPH(OCH3))2, AN UNUSUAL PSEUDOCLATHROCHELATE COMPLEX, AND RE(III)CL(CDO)(CDOH)2BPH

A number of uncapped and monocapped rhenium(III) complexes and a biscapped manganese(II) tris(dioxime) complex have been synthesized and fully characterized. The uncapped rhenium(III) tris(dioxime) complexes, ReCl(dioximeH)2(dioximeH2), are neutral, seven-coordinate complexes with a chloride occupying the seventh site. They can be capped at one end with a boronic acid to give ReCl(dioxime)(dioximeH)2BR. These complexes are analogous to the previously reported technetium BATO complexes. 1,2 The Mn(II) complex is neutral, six-coordinate, and biscapped with a tetrahedral boron derivative bound at each end to only two of the three oximes. ReCl(CDO)(CDOH)2BPh.1/2C6H14 (CDOH2 = 1,2-cyclohexanedione dioxime), ReClC24H31N6O6B.1/2C6H14, crystallizes from CH2Cl2/hexane (1:1) in the triclinic space group P1BAR with a = 12.393 (2) angstrom, b = 13.350 (4) angstrom, c = 11.539 (4) angstrom, alpha = 115.14 (2) - degrees, beta = 113.53 (2)-degrees, gamma = 92.63 (2)-degrees, Z = 2, R = 0.050, and R(w) = 0.058. Mn(CDO)(CDOH)2(BPh(OCH3))2, MnC32H42N6O8B2, crystallizes from CH2Cl2/MeOH (1:1) in the triclinic space group P1BAR with a = 11.804 (1) angstrom, b = 15.155 (1) angstrom, c = 10.609 (1) angstrom, alpha = 105.45 (1)-degrees, beta = 103.70 (1)-degrees, gamma = 98.70 (1)-degrees, Z = 2, R = 0.044, and R(w) = 0.050.