School of Chemistry, Monash University, P.O. Box 23, Melbourne, VIC, 3800, Australia.
Chem Asian J. 2019 Feb 1;14(3):486-490. doi: 10.1002/asia.201801800. Epub 2019 Jan 16.
Reactions of the beryllium dihalide complexes [BeX (OEt ) ] (X=Br or I) with N,N,N',N'-tetramethylethylenediamine (TMEDA), a series of diazabutadienes, or bis(diphenylphosphino)methylene (DPPM) have yielded the chelated complexes, [BeX (TMEDA)], [BeX {(RN=CH) }] (R=tBu, mesityl (Mes), 2,6-diethylphenyl (Dep) or 2,6-diisopropylphenyl (Dip)), and the non-chelated system, [BeI (κ -P-DPPM) ]. Reactions of lithium or potassium salts of a variety of β-diketiminates have given both three-coordinate complexes, [{HC(RCNAr) }BeX] (R=H or Me; Ar=Mes, Dep or Dip; X=Br or I); and four-coordinate systems, [{HC(MeCNPh) }BeBr(OEt )] and [{HC(MeCNDip)(MeCNC H NMe }BeI]. Alkali metal salts of ketiminate, guanidinate, boryl/phosphinosilyl amide, or terphenyl ligands, lead to dimeric [{BeI{μ-[(OCMe)(DipNCMe)]CH}} ], and monomeric [{iPr NC(NMes) }BeI(OEt )], [κ -N,P-{(HCNDip) B}(PPh SiMe )NBeI(OEt )] and [{C H Ph -2,6}BeBr(OEt )], respectively. Compound [{HC(MeCNPh) }BeBr(OEt )] undergoes a Schlenk redistribution reaction in solution, affording the homoleptic complex, [{HC(MeCNPh) } Be]. The majority of the prepared complexes have been characterized by X-ray crystallography and multi-nuclear NMR spectroscopy. The structures and stability of the complexes are discussed, as is their potential for use as precursors in poorly developed low oxidation state beryllium chemistry.
二卤化铍配合物[BeX（OEt）]（X=Br 或 I）与 N，N，N'，N'-四甲基乙二胺（TMEDA）、一系列二氮杂丁二烯或双（二苯基膦）亚甲基（DPPM）的反应生成了螯合配合物[BeX（TMEDA）]、[BeX{（RN=CH）}]（R=tBu、mesityl（Mes）、2,6-二乙基苯基（Dep）或 2,6-二异丙基苯基（Dip））和非螯合体系[BeI（κ-P-DPPM）]。各种β-二酮亚胺盐的锂或钾盐的反应给出了三配位配合物[{HC（RCNAr）}BeX]（R=H 或 Me；Ar=Mes、Dep 或 Dip；X=Br 或 I）和四配位体系[{HC（MeCNPh）}BeBr（OEt）]和[{HC（MeCNDip）（MeCNCHNMe）}BeI]。酮亚胺盐、胍亚胺盐、硼/膦酰基酰胺或三联苯配体的碱金属盐导致二聚体[{BeI{μ-[(OCMe）（DipNCMe）]CH}}]，和单体[{iPrNC（NMes）}BeI（OEt）]、[κ-N，P-（（HCNDip）B）（PPhSiMe）NBeI（OEt）]和[{C H Ph-2,6}BeBr（OEt）]，分别。化合物[{HC（MeCNPh）}BeBr（OEt）]在溶液中经历施伦克重排反应，生成均配体配合物[{HC（MeCNPh）}Be]。大多数制备的配合物都通过 X 射线晶体学和多核 NMR 光谱学进行了表征。讨论了配合物的结构和稳定性，以及它们作为欠发达的低氧化态铍化学前体的潜在用途。
