Abstractη3-Allylhydrogensulfidonickel (2) reacts with n-butyllithium with elimination of lithium sulfide and formation of the ionic η3-allylnickel-sulfur-cluster [(η3-C3H5Ni)3S2]+[Li(THF)2]- (4). The crystal structure of the analogous THF-TMEDA-adduct (4′) indicates that the nickel and sulfur atoms of the anion adopt a trigonal bipyramidal arrangement, in which the sulfur atoms are at the apices of the bipyramid. The Li(THF)2+ cation in 4 can be replaced by the (n-C4H9)4N+ cation (5). The 1H NMR spectra suggest the presence of two stereoisomers of the anionic clusters in 4 and 5 having C3h and Cs symmetry. In the reaction of η3-allyl- or η3-methallylhydrogensulfidopalladium (6, 6 a) with n-butyl-lithium crystalline compounds having the composition RC3H4PdSLi(THF)≈4, R = H, CH3 (7, 7 a) are obtained; their 1H NMR spectra also reveal the existence of the two stereoisomers having C3h and Cs symmetry. The same type of stereoisomerism is observed with the crystalline [(n-C4H9)4N]+[(η3-C3H5Pd)3S2]- (8) obtained from 7 and (n-C4H9)4N+ClO4-. For 7 and 7 a an ionic structure consisting of trigonal bipyramidal (η3-RC3H4Pd)3S2- anions and Li3S(THF)4+ cations is proposed.
Hydrogen bonded networks based on hexarhenium(iii) chalcocyanide cluster complexes: structural and photophysical characterization
