Molecular structures of (tBu)Ga(S2CNnPr2)2 and (iPrO)Ga(S2CNEt2)2: An example of an unusual ligand pseudorotation

The molecular structures of (^tBu)Ga(S₂CNⁿPr₂)₂ (1) and (ⁱPrO)Ga(S₂CNEt₂)₂ (2) have been determined. The variation in the geometries observed for bis-dithiocarbamate compounds of gallium, (X)Ga(S₂CNMe₂)₂ (X=Cl, ⁱPrO, ^tBu) do not lie along the Berry pseudorotation pathway for the square-based pyramid to trigonal bipyramid geometrical transition. Instead, the structures appear to lie on an unusual ligand two-step, Texas, pseudorotation mechanism which results in a highly distorted trigonal bipyramidal geometry. Crystal data: (1) monoclinic, P2₁,/c, a = 9.786(1), b = 29.218(3), c = 9.452(1) Å, = 108.379(9)°, V = 2564.7(5) ų, and Z = 4. (2) Monoclinic, P2₁ /c, a = 10.980(3), b = 15.673(4), c = 12.461(3) Å, = 97.47(2)°, V = 2126.2(9) ų and Z = 4.     

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