TY - JOUR
T1 - Beryllium Halide Complexes Incorporating Neutral or Anionic Ligands
T2 - Potential Precursors for Beryllium Chemistry
AU - Paparo, Albert
AU - Jones, Cameron
PY - 2019/2/1
Y1 - 2019/2/1
N2 - 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(κ1-P-DPPM)2]. Reactions of lithium or potassium salts of a variety of β-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{μ-[(OCMe)(DipNCMe)]CH}}2], and monomeric [{iPr2NC(NMes)2}BeI(OEt2)], [κ2-N,P-{(HCNDip)2B}(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}2Be]. 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.
AB - 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(κ1-P-DPPM)2]. Reactions of lithium or potassium salts of a variety of β-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{μ-[(OCMe)(DipNCMe)]CH}}2], and monomeric [{iPr2NC(NMes)2}BeI(OEt2)], [κ2-N,P-{(HCNDip)2B}(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}2Be]. 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.
KW - beryllium
KW - low oxidation state
KW - reduction
KW - steric bulk
KW - β-diketiminate
UR - http://www.scopus.com/inward/record.url?scp=85060177934&partnerID=8YFLogxK
U2 - 10.1002/asia.201801800
DO - 10.1002/asia.201801800
M3 - Article
AN - SCOPUS:85060177934
SN - 1861-4728
VL - 14
SP - 486
EP - 490
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 3
ER -