226945-50-2Relevant academic research and scientific papers
A dynamic NMR study of sulphur inversion in transition metal complexes of 2,6-dithiaspiro[3.3]heptane (2,6-DTSH), 2,6-DTSH-2-oxide and 2,6-DTSH-2,2-dioxide
Abel, Edward W.,Orrell, Keith G.,Poole, Mark C.,Sik, Vladimir
, p. 1345 - 1353 (1999)
The following complexes were synthesised [W(CO)5L1], [{W(CO)5}2L1], [W(CO)5L2], [W(CO)5L3], [{PdCl2(PPh3)}2L1], [PdCl2(PPh3)L2] and [PdCl2(PPh3)L3] where L1=2,6-dithiaspiro[3.3]heptane (2,6-DTSH), L2=2,6-DTSH-2-oxide and L3=2,6-DTSH-2,2′-dioxide. In solution these complexes exhibit pyramidal inversion of the metal-coordinated sulphur atom(s), rates and activation energies of which were evaluated by total NMR bandshape analysis. ΔG? values were in the range 45-50 kJ mol-1. These magnitudes are discussed in terms of ring geometry distortions and sulphur lone pair interactions.
