Sulphur chelates 33. Preparation, characterization and x-ray structure determination of (chloro)(pentane-2,4-dithionato)(triethylphosphine)nickel(II), Ni(SacSac)(PEt3)Cl, an asymmetric complex which displays fluxional behavior in solution on the NMR time scale
✍ Scribed by John P. Fackler Jr.; A.F. Masters
- Publisher
- Elsevier Science
- Year
- 1980
- Tongue
- English
- Weight
- 732 KB
- Volume
- 39
- Category
- Article
- ISSN
- 0020-1693
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✦ Synopsis
The title compound has been prepared and characterized spectroscopically and by single-crystal X-ray crystallography (refined to R1 = 0.052, R, = 0.064 with I837 data having I > 30(I)). The dithioacetylacetonate (SacSac) methyl groups are NMR equivalent at room temperature, but can be resolved at temperatures below 288 K. The compound crystallizes in the monoclinic
space group P2,fn with a = 7.6107(3) A, b = 18.1466(28) A and c= Il.5270(5) A; fl = 98.459(3/O, V = 1574.12(25) A3, and 2 = 4. The coordination about the nickel(H) is planar. Important nickel-iigand lengths are Ni-S (tram Cl) 2.108(2) A, Ni-S (trans P) 2.154(2) A, Ni-cir 2.206(2) A, Ni-P 2.232(2) A with angles SNiS 97.9(l)", SNiCl 85.6(l)", SNiP 91.4(l)" and ClNiP 85.2(I)'. Two of the triethylphosphine ethyl groups lie in a plane approximately normal to the rest of the molecule. The dithioacetylacetonate dimensions are similar to those in Ni(SacSac),, although the chelate bite is smaller, and there may be some asymmetry in the CS bonding in Ni(Sac&c)PEtJl, i%e molecules pack with their chelate rings approximately parallel.