摘要/Abstract
合成了5种不同取代基的炔类化合物Mes2HSiC≡CPh (1, Mes=2,4,6-Me3C6H2)、[tBuC(NAr)2]GeC≡CPh (2, Ar=2,6-iPr2C6H3)、[PhC(NtBu)2]SnC≡CPPh2 (3)、[HC(CMe)2(NAr)2]SnC≡CPPh2 (4)和[HC(CMe)2(NAr)2]ZnC≡CPPh2 (5), 研究了这些化合物与B(C6F5)3的反应. 在与B(C6F5)3的反应中, 1和2均发生1,1-碳硼化反应生成烯烃化合物(Ph)(Mes2HSi)C=C(C6F5)B(C6F5)2 (6)和{[tBuC(NAr)2]Ge}(Ph)C=C(C6F5)B(C6F5)2 (7), 7是一种GeII/B松散Lewis酸碱对化合物; 3~5则都发生B(C6F5)3与配体金属基的位置交换、进而配体金属基转换键合PPh2的反应, 分别生成新颖的分子内双性离子炔烃化合物[PhC(NtBu)2]SnP(Ph2)C≡CB(C6F5)3(8)、[HC(CMe)2(NAr)2]SnP(Ph2)C≡CB(C6F5)3 (9)、[HC(CMe)2(NAr)2]ZnP(Ph2)C≡CB(C6F5)3 (10). 文中还讨论了反应机理.
关键词: 新型取代基炔烃, B(C6F5)3, 1,1-碳硼化反应, 基团转换反应, 新型取代基烯烃
Five alkyne compounds of varied novel substituents as Mes2HSiC≡CPh (1, Mes=2,4,6-Me3C6H2), [tBuC- (NAr)2]GeC≡CPh (2, Ar=2,6-iPr2C6H3), [PhC(NtBu)2]SnC≡CPPh2 (3), [HC(CMe)2(NAr)2]SnC≡CPPh2, (4) and [HC(C- Me)2(NAr)2]ZnC≡CPPh2 (5) have been synthesized. Compounds 1 and 2 reacted with B(C6F5)3 by the 1,1-carboboration to give compounds (Ph)(Mes2HSi)C=C(C6F5)B(C6F5)2 (6) and {[tBuC(NAr)2]Ge}(Ph)C=C(C6F5)B(C6F5)2 (7), respectively, where (F5C6)3B/Mes2HSi group exchange was suggested to occur initially for the former reaction while the (F5C6)3B/ [tBuC(NAr)2]Ge exchange was for the latter one. Compound 6 is a acyclic alkene whereas 7 is viewed as a germanaboracyclo- butene owing to a strong GeII→B donor-acceptor bonding being a GeII/B frustrated Lewis pair (FLP). Compounds 3~5 reacted with B(C6F5)3 to undergo a ligand coordinated metal group/B(C6F5)3 exchange followed by bonding of metal group at PPh2, resulting in the formation of a novel type of intramolecular zwitterionic alkynes [PhC(NtBu)2]SnP(Ph2)C≡CB(C6F5)3(8), [HC(CMe)2(NAr)2]SnP(Ph2)C≡CB(C6F5)3 (9), and [HC(CMe)2(NAr)2]ZnP(Ph2)C≡CB(C6F5)3 (10), respectively. Compounds 1~10 have been characterized by spectroscopy and elemental analysis, of which 4, 6, 7, and 10 are further authenticated by X-ray crystallography. The mechanisms of these reactions are discussed.
Key words: alkynes of novel substituents, B(C6F5)3, 1,1-carboboration, group exchange reaction, alkenes of novel substituents
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