4.6 Article

Beryllium Halide Complexes Incorporating Neutral or Anionic Ligands: Potential Precursors for Beryllium Chemistry

Journal

CHEMISTRY-AN ASIAN JOURNAL
Volume 14, Issue 3, Pages 486-490

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/asia.201801800

Keywords

beryllium; low oxidation state; reduction; steric bulk; beta-diketiminate

Funding

  1. Australian Research Council
  2. US Air Force Asian Office of Aerospace Research and Development [FA2386-18-1-0125]
  3. Alexander von Humboldt Foundation

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Reactions of the beryllium dihalide complexes [BeX2(OEt2)(2)] (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, [BeX2(TMEDA)], [BeX2{(RN=CH)(2)}] (R=tBu, mesityl (Mes), 2,6-diethylphenyl (Dep) or 2,6-diisopropylphenyl (Dip)), and the non-chelated system, [BeI2(kappa(1)-P-DPPM)(2)]. Reactions of lithium or potassium salts of a variety of beta-diketiminates have given both three-coordinate complexes, [{HC(RCNAr)(2)}BeX] (R=H or Me; Ar=Mes, Dep or Dip; X=Br or I); and four-coordinate systems, [{HC(MeCNPh)(2)}BeBr(OEt2)] and [{HC(MeCNDip)(MeCNC2H4NMe2}BeI]. Alkali metal salts of ketiminate, guanidinate, boryl/phosphinosilyl amide, or terphenyl ligands, lead to dimeric [{BeI{mu-[(OCMe)(DipNCMe)]CH}}(2)], and monomeric [{iPr(2)NC(NMes)(2)}BeI(OEt2)], [kappa(2)-N,P-{(HCNDip)(2)B}(PPh2SiMe2)NBeI(OEt2)] and [{C6H3Ph2-2,6}BeBr(OEt2)], respectively. Compound [{HC(MeCNPh)(2)}BeBr(OEt2)] undergoes a Schlenk redistribution reaction in solution, affording the homoleptic complex, [{HC(MeCNPh)(2)}(2)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.

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