当前位置: X-MOL 学术J. Organomet. Chem. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Synthesis and structure of annulated dithieno[2,3-b;3ʹ,2ʹ-d]thienyl- and ring-opened 3,3ʹ-bithienyl Fischer carbene complexes
Journal of Organometallic Chemistry ( IF 2.3 ) Pub Date : 2020-08-11 , DOI: 10.1016/j.jorganchem.2020.121466
Zandria Lamprecht , Frederick P. Malan , David C. Liles , Simon Lotz , Daniela I. Bezuidenhout

Nucleophilic attack on the central sulphur of dithieno[2,3-b;3ʹ,2ʹ-d]thiophene (DTT) by n-BuLi opens the central thiophene ring and afforded, after subsequent reaction with Cr(CO)6 and alkylation with [Et3O][BF4], a series of mono- and biscarbene complexes containing a 3,3ʹ-dithienyl backbone with a SBu substituent. Repeating the reaction with diisopropylamine as the nucleophile, leads to a dihydrodesulphurization reaction with ring-opening of the central thiophene ring of DTT and elimination of the sulphur atom. Subsequent reaction with n-BuLi or LDA, Cr(CO)6 and [Et3O][BF4] afforded 3,3ʹ-dithienyl mono- and biscarbene complexes. In both instances α,αʹ-dithienothiophene biscarbene complex was observed spectroscopically but not isolated. By using α,αʹ-dibromodithieno[2,3-b;3ʹ,2ʹ]thiophene as substrate, improved yields of the targeted mono- and biscarbene complexes of [2,3-b;3ʹ,2ʹ-d]-DTT (M=Cr, W) could be obtained. The biscarbene complexes were unstable in the reaction mixture but in the case of tungsten could be isolated after in situ aminolysis with dimethylamine. The use of KHMDS as base converted Cr(CO)6 to K[Cr(CO)5(CN)] and after reaction with DTT and subsequent alkylation with [Et3O][BF4], afforded the chromium tetracarbonyl carbene complex of DTT.



中文翻译:

环状双噻吩并[2,3- b ; 3ʹ,2ʹ- d ]噻吩基和开环的3,3ʹ-噻吩基卡菲配合物的合成与结构

n -BuLi对二噻吩并[2,3- b ; 3ʹ,2ʹ- d ]噻吩(DTT)的中心硫进行亲核攻击,打开中心噻吩环,并随后与Cr(CO)6反应并与[ Et 3 O] [BF 4 ],一系列含有3,3′-二噻吩基骨架和SBu取代基的单和双卡宾配合物。用二异丙胺作为亲核试剂重复该反应,导致二氢脱硫反应,其中DTT的中央噻吩环开环并消除了硫原子。随后与丁基锂或LDA,Cr(CO)6和[Et 3 O] [BF 4得3,3′-二噻吩基单-和双卡宾配合物。在两种情况下,均能通过光谱法观察到α,αʹ-二硫代噻吩双卡宾配合物,但未分离。通过使用α,αʹ-二溴二噻吩并[2,3- b ; 3ʹ,2ʹ]噻吩作为底物,可以提高[2,3- b; 可以得到3ʹ,2ʹ- d ] -DTT(M = Cr,W)。双卡宾配合物在反应混合物中不稳定,但在用二甲胺原位氨解后可以分离出钨的情况下。使用KHMDS作为碱将Cr(CO)6转化为K [Cr(CO)5(CN)],并与DTT反应并随后与[Et 3 O] [BF 4进行烷基化,得到DTT的铬四羰基卡宾络合物。

更新日期:2020-08-23
down
wechat
bug