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The reactions of [HB(pz)3ReOCl2] (1) with chelating hydrazines were studied. In contrast to the common substitution pattern which occurs through a condensation type reaction to displace the oxo group in forming the metal-hydrazido functionality, 1 reacts with hydrazinophthalazine (hydralazine) to give [HB(pz)3ReO(HNNC8H5N2)] (2). Similarly, reaction with bishydrazinophthalazine produces the binuclear species [{HB(pz)3ReO}2{(HNN)2C8H4N2}] (3). The relative ease of substitution of the chloride groups in 1 is evident in the reactions of 1 with thiolate donors to yield complexes of the type [HB(pz)3ReO(2-pyridinthiol)2] (4). Crystal data: 2 · CH2Cl2, monoclinic P2 1 /c, a = 12.820(3), b = 11.616(2), c = 15.626(3) A , β = 104.93(3)°, V = 2248(1) A 3 , Z = 4, D calc = 1.171 g cm −3 ; structure solution and refinement based on 2316 reflections converged at R = 0.0395. 4 · 1.5CH2Cl2, triclinic P 1 , a = 10.181(2), b = 14.159(3), c = 9.622(2) A , α = 95.51(3), β = 93.25(3), γ = 88.18(3)°, V = 1377.9(7) A 3 , Z = 2, D calc = 1.718 g cm −3 ; R = 0.0351 for 3291 reflections. |
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