Synthesis of Heavier Group 14 Metal Compounds from 2,6-Lutidylbis(phosphoranosulfide)

The synthesis and characterization of various novel group 14 metal compounds derived from 2,6-lutidylbisphosphoranosulfide, [(SPPri2CH2)2C5H3N-2,6] (1), are reported. The monoanionic bis(thiophosphinoyl) lithium complex [Li{(SPPri2CH)(SPPri2CH2)C5H3N-2,6}(Et2O)] (2) has been prepared from the reaction of 1 with an equimolar amount of nBuLi in THF. Treatment of 1 with 1 equiv of M{N(SiMe3)2}2 (M = Sn, Pb) afforded the 1,3-distannacyclobutane [{2-{Sn{C(Pri2PS)}}-6-{CH2(Pri2PS)}}C5H3N]2 (3) and 1,3-diplumbacyclobutane [{2-{Pb{C(Pri2PS)}}-6-{CH2(Pri2PS)}}-C5H3N]2 (4), respectively. The metathesis reaction of 2 with GeCl2·(dioxane) and SnCl2 gave the unexpected digermylgermylene Ge[GeCl2{(SPPri2CH)(SPPri2CH2)C5H3N-2,6}]2 (5) and ionic [2,6-lutidylbis(thiophosphinoyl)methanide]tin(II) trichlorostannate [{C5H3N-2,6-(CH2PPri2S)(CHPPri2S)}Sn]+[SnCl3]− (6), respectively. The X-ray structures of 2−6 have been determined by X-ray crystallography.