Unraveling the Mechanism of 1,3-Diyne Cross-Metathesis Catalyzed by Silanolate-Supported Tungsten Alkylidyne Complexes
作者:Tobias M. Schnabel、Daniel Melcher、Kai Brandhorst、Dirk Bockfeld、Matthias Tamm
DOI:10.1002/chem.201801651
日期:2018.6.26
benzylidyne complex [PhC≡WOSi(OtBu)3}3] (1) catalyzed the cross‐metathesis between 1,4‐bis(trimethylsilyl)‐1,3‐butadiyne (2) and symmetrical 1,3‐diynes (3) efficiently, which gave access to TMS‐capped 1,3‐diynes RC≡C−C≡CSiMe3 (4). Diyne cross‐metathesis (DYCM) studies with 13C‐labeled diyne PhC≡13C−13C≡CPh (3*) revealed that this reaction proceeds through reversible carbon–carbon triple‐bond cleavage and formation
亚苄基配合物[PhC≡WOSi(O t Bu)3 } 3 ](1)催化1,4-双(三甲基甲硅烷基)-1,3-丁二炔(2)与对称1,3-的交叉复分解二炔(3)有效地,这给了访问TMS封端的1,3-二炔RC≡C-C≡CSiMe 3(4)。二炔交叉复分解(DYCM)与研究13 C标记的二炔PhC≡ 13 C- 13 C≡CPh(3 *)显示,该反应通过可逆碳-碳三键断裂和形成前进根据炔的常规机制复分解。1之间的反应和3 *,得到3- phenylpropynylidyne复杂PhC≡ 13 C- 13 C≡WOSi的(O吨丁基)3 } 3 ](5 *),表明alkynylalkylidyne络合物可能用作催化活性物质。企图孤立5 *从的混合物1和3个*得到的二钨2-丁炔-1,4- diylidyne配合物[(晶体吨迪布奥)3的SiO} 3 W≡ 13 C- 13 C≡ 13 C- 13 C≡