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

Abstract

The reactivity of neodymium diiodide, 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)2O (19 %). The reaction with Et3SiBr in THF results in formation of Et3SiSiEt3 (17 %) and Et3SiOBun (34 %). Alkylation of Me3SiCl with PrnCl in the presence of 1 in THF affords Me3SiPrn (10 %), Me3SiOBun (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 1 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.

[AnI3(THF)4] (An = Np, Pu) Preparation Bypassing An0 Metal Precursors: Access to Np3+/Pu3+ Nonaqueous and Organometallic Complexes

“…The trivalent iodides 3-Np and 3-Pu both crystallized in the monoclinic space group P2 1 /c and are isomorphous with several other early f-block halides such as the U-congener, 3-U, 40,41 as well as Ln analogues 3-La, 91 3-Ce, 92 3-Pr, 93 3-Nd. 94 Table 1 reveals a pattern in M−I bond lengths for the 3-M series whereby the lengths decrease from U > Np > Pu on average and the Ln−I lengths for La and Ce are significantly longer than for An−I lengths for An 3+ ions with comparable ionic radii. In this series, the bond lengths follow a previously noted trend of soft-donor ligands (such as I) exhibiting shorter bonds with An 3+ ions than Ln 3+ ions of comparable radii, and this is often proposed to arise from the greater covalent character in the An−ligand bond.…”

“…The trivalent iodides 3-Np and 3-Pu both crystallized in the monoclinic space group P 2 1 / c and are isomorphous with several other early f-block halides such as the U-congener, 3-U , , as well as Ln analogues 3-La , 3-Ce , 3-Pr , 3-Nd Table reveals a pattern in M–I bond lengths for the 3-M series whereby the lengths decrease from U > Np > Pu on average and the Ln–I lengths for La and Ce are significantly longer than for An–I lengths for An 3+ ions with comparable ionic radii.…”

Structural characterization of methanol substituted lanthanum halides

“…[38–40, 83, 91–116] While these complexes ranged in nuclearity, the majority were monomers adopting a 2IS/1OS arrangement [(L) x LnI 2 ](I)[38, 40, 91–96, 106, 111, 117] (where L = neutral ligand or organic solvents such as: Pr i OH,[38] THF,[106, 117] and py[38, 106]) or the 3IS arrangement that utilizes combinations of bulky neutral ligands,[83, 95, 107, 110, 114, 118] THF,[98, 100, 102, 113] or Pr i OH [39] to fill the coordination sphere. However, no structure reports of the LaI 3 •MeOH derivatives have been previously reported.…”

Small-Scale Metal-Based Syntheses of Lanthanide Iodide, Amide, and Cyclopentadienyl Complexes as Analogues for Transuranic Reactions

“…As an alternative to the published procedure , following the procedure for 3-La , NdI 3 (OEt 2 ) 0.66 (13 mg, 0.023 mmol) was dissolved in THF (3 mL) to give NdI 3 (THF) 4 (16 mg, quantitative) as a pale blue solid. Pale blue X-ray-quality crystals of 3-Nd were grown over 2 weeks from a hot THF solution cooled to −30 °C, which matched the unit cell of NdI 3 (THF) 4 …”

“…Pale blue X-ray-quality crystals of 3-Nd were grown over 2 weeks from a hot THF solution cooled to −30 °C, which matched the unit cell of NdI 3 (THF) 4 . 81 1 H NMR (C 6 D 6 ): δ 3.78 (s, br ν 1/2 115 Hz, THF), 1.60 (s, br ν 1/2 100 Hz, THF).…”