Use of Neodymium Diiodide in the Synthesis of Organosilicon, ‐Germanium and ‐Tin Compounds

The reactivity of neodymium diiodide, NdI 2 ( 1 ), towards organosilicon, ‐germanium and ‐tin halides has been investigated. Compound 1 readily reacts with Me 3 SiCl in DME to give trimethylsilane (6 %), hexamethyldisilane (4 %) and (Me 3 Si) 2 O (19 %). The reaction with Et 3 SiBr in THF results in formation of Et 3 SiSiEt 3 (17 %) and Et 3 SiOBu n (34 %). Alkylation of Me 3 SiCl with Pr n Cl in the presence of 1 in THF affords Me 3 SiPr n (10 %), Me 3 SiOBu n (52 %) and Me 3 SiSiMe 3 (1 %). The main product identified in the reaction mixture formed upon interaction of 1 with dichlorodimethylsilane Me 2 SiCl 2 in THF is di‐ n ‐butoxydimethylsilane Me 2 Si(OBu n ) 2 (54 %) together with minor amounts of Me 2 Si(OBu n )Cl. The reaction of 1 with Me 3 GeBr under the same conditions produces Me 3 GeGeMe 3 (44 %), Me 3 GeH (3 %), and Me 3 GeI (7 %). An analogous set of products was obtained in the reaction with Et 3 GeBr. Treatment of trimethyltin chloride with 1 causes reduction of the former to tin metal (74 %). Me 3 SnH (7 %) and hexamethyldistannane (11 %) were identified in the volatile products. The reaction of 1 with Me 3 SiI provides straightforward access to hepta‐coordinated NdI 3 (THF) 4 ( 2 ), the structure of which was determined by X‐ray diffraction.