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Distannabarrelenes with Three Coordinated SnII Atoms
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-03-26 , DOI: 10.1002/chem.202001432
Mahendra K Sharma 1 , Timo Glodde 1 , Beate Neumann 1 , Hans-Georg Stammler 1 , Rajendra S Ghadwal 1
Affiliation  

Crystalline 1,4‐distannabarrelene compounds [(ADCAr)3Sn2]SnCl3 (3Ar) (ADCAr={ArC(NDipp)2CC}; Dipp=2,6‐iPr2C6H3, Ar=Ph or DMP; DMP=4‐Me2NC6H4) derived from anionic dicarbenes Li(ADCAr) (2Ar) (Ar=Ph or DMP) have been reported. The cationic moiety of 3Ar features a barrelene framework with three coordinated SnII atoms at the 1,4‐positions, whereas the anionic unit SnCl3 is formally derived from SnCl2 and chloride ion. The all carbon substituted bis‐stannylenes 3Ar have been characterized by NMR spectroscopy and X‐ray diffraction. DFT calculations reveal that the HOMO of 3Ph (ϵ=−6.40 eV) is mainly the lone‐pair orbital at the SnII atoms of the barrelene unit. 3Ar readily react with sulfur and selenium to afford the mixed‐valence SnII/SnIV compounds [(ADCAr)3SnSn(E)](SnCl6)0.5 (E=S 4Ar, Ar=Ph or DMP; E=Se 5Ph).

中文翻译:


具有三个配位 SnII 原子的 Distannabarrelene



结晶1,4-二锡桶烯化合物[(ADC Ar ) 3 Sn 2 ]SnCl 3 ( 3Ar ) (ADC Ar ={ArC(NDipp) 2 CC}; Dipp=2,6‐ i Pr 2 C 6 H 3 , Ar=Ph 或 DMP;DMP=4-Me 2 NC 6 H 4 ) 衍生自阴离子二碳烯 Li(ADC Ar ) ( 2 -Ar ) (Ar=Ph 或 DMP)。 3 - Ar的阳离子部分具有在 1,4 位上具有三个配位 Sn II原子的桶烯骨架,而阴离子单元 SnCl 3形式上源自 SnCl 2和氯离子。全碳取代的双亚锡基3 - Ar已通过 NMR 光谱和 X 射线衍射进行了表征。 DFT 计算表明3Ph ( ϵ =−6.40 eV) 的 HOMO 主要是桶烯单元 Sn II原子处的孤对轨道。 3Ar很容易与硫和硒反应生成混合价 Sn II /Sn IV化合物 [(ADC Ar ) 3 SnSn(E)](SnCl 6 ) 0.5 (E=S 4 ‐Ar , Ar=Ph 或 DMP ; E=Se 5 - Ph )。
更新日期:2020-03-26
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