Use of neodymium diiodide in the synthesis of organosilicon, -germanium and -tin compounds

The reactivity of neodymium chiodide, NdI2 (1), towards organosilicon, -germanium and -tin halides has been investigated. Compound 1 readily reacts with Me3SiCl in DME to give trimethylsilane (6 %), hexamethyldisilane (4 %) and (Me3Si)(2)O (19%). The reaction with Et3SiBr in THF results in formation of Et3SiSiEt3 (17 %) and Et3SiOBun (34 %). Alkylation Of Me3SiCl with (PrCl)-Cl-n in the presence of 1 in THF affords Me3SiPrn (10 %), MC3SiOBun (52%) and Me3SiSiMe3 (1 %). The main product identified in the reaction mixture formed upon interaction of 1 with dichlorodimethylsilane Me2SiCl2 in THF is di-n-butoxydimethylsilane Me2Si(OBUn)(2) (54%) together with minor amounts of Me2Si(OBun)Cl. The reaction of 1 with Me3GeBr under the same conditions produces Me3GeGeMe3 (44 %), Me3GeH (3 %), and Me3GeI (7 %). An analogous set of products was obtained in the reaction with Et3GeBr. Treatment of trimethyltin chloride with I causes reduction of the former to tin metal (74 %). Me3SnH (7 %) and hexamethyldistannane (11 %) were identified in the volatile products. The reaction of 1 with Me3SiI provides straightforward access to hepta-coordinated NdI3(THF)(4) (2), the structure of which was determined by X-ray diffraction.