Exploring Synthetic Routes to Heteroleptic UIII, UIV, and ThIV Bulky Bis(silyl)amide Complexes
Conrad A. P. Goodwin; Floriana Tuna; Eric J. L. McInnes; David P. Mills
文献索引：10.1002/ejic.201800036
全文：HTML全文
摘要
The bis(silyl)amide {N(SiMe3)2} (N′′) has supported spectacular actinide (An) chemistry for over 40 years, yet surprisingly there are only a handful of An complexes containing larger bis(silyl)amides, for example [U(N**)3] [N** = {N(SiMe2tBu)2}, 1]. Herein we report the structural characterization of the UIII complexes [U(N**)2(µ‐I)]2 (2), [U(N†′)2(µ‐I)]2 [N†′ = {N(SiiPr3)(SiMe3)}, 3], [U(N††)(I)2(THF)2] [N†† = {N(SiiPr3)2}, 4], [U(N††)2(I)] (5), and [U(N†′)2(I)(THF)] (6), and the AnIV complexes [An(N**){N(SiMe2tBu)(SiMetBuCH2‐κ2‐N,C)}(µ‐Cl)]2 (7‐An, An = U, Th) and [Th(N**)2{N(SiMe2tBu)(SiMetBuCH2‐κ2‐N,C)}] (8). Low crystalline yields were obtained in all cases, presumably due to facile cyclometallation. Although this precluded full characterization of UIII 4 and 6, and AnIV 7 and 8, for UIII complexes 2, 3, and 5 yields were high enough to perform NMR, EPR, NIR/UV/Vis, and FTIR spectroscopy, elemental analysis, and magnetic measurements.