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Synthesis, Structure, and Reactivity of Gold(I) α-Oxo Carbenoid Complexes
Organometallics ( IF 2.8 ) Pub Date : 2020-03-24 , DOI: 10.1021/acs.organomet.0c00033
Caroline P. Stow 1 , Ross A. Widenhoefer 1
Affiliation  

The trifluoromethanesulfonate α-oxo carbenoid complexes (IPr)AuCH(OTf)COR [R = OEt (1a), p-tolyl (1b)] were isolated from reactions of (IPr)Au(OTf) with the corresponding α-diazo carbonyl compounds. The pyridinium α-oxo carbenoid complexes [(IPr)AuCH(4-MeC5H4N)COR]+OTf (2), the sulfonium α-oxo carbenoid complexes [(IPr)AuCH(SR′2)COR]+OTf [3 (R′ = Me), 4 (R′ = Ph)], and the α,α-dioxo carbenoid complexes [(IPr)AuC(R)(CO2Me)2]+OTf [R = 4-MeC5H4N (5), R = SPh2 (6)] were synthesized either via reaction of complexes 1 with 4-picoline or dimethyl sulfide or via reaction of (IPr)Au(OTf) with stabilized ylides. Complexes 16 were thermally stable and were characterized in solution and, in the cases of complexes 2 and 3, by single-crystal X-ray diffraction. Complex 1b underwent carbene transfer to cyclohexene in modest yield at 75 °C. The pyridinium and sulfonium α-oxo carbenoid complexes 2 and 3 displayed no reactivity toward dimethyl sulfide, 4-picoline, 1-octyne, or p-methoxystyrene. Complex 5 underwent rapid displacement of the ylide ligand in the presence of dimethyl sulfide or 4-picoline. Taken together, we obtained no evidence suggesting that these sulfonium or pyridinium α-oxo carbenoid complexes might behave as α-oxo carbene surrogates.

中文翻译:

金(I)α-氧代类胡萝卜素配合物的合成,结构和反应性

从(IPr)Au(OTf)与相应的α-重氮羰基化合物的反应中分离出三氟甲磺酸盐α-氧代羰基化合物(IPr)AuCH(OTf)COR [R = OEt(1a),甲苯基(1b)] 。吡啶鎓α氧代卡宾配合物[(IPR)AUCH(4-MEC 5 ħ 4 N)COR] +光学传递函数- 2),锍α氧代卡宾配合物[(IPR)AUCH(SR' 2)COR] + OTf [ 3(R'= Me),4(R'= Ph)],和α,α-二氧羰类化合物[(IPr)AuC(R)(CO 2 Me)2 ] +OTf [R = 4-MeC 5 H 4 N(5),R = SPh 26)]是通过配合物1与4-甲基吡啶或二甲硫醚反应或通过(IPr)Au(OTf)反应合成的与稳定的乙炔。配合物1 - 6是热稳定的并且其特征在于,溶液,并且在复合物的情况下,23,通过单晶X射线衍射。配合物1b在75°C下以适度收率进行卡宾转移至环己烯。吡啶鎓和sulf鎓α-氧代类胡萝卜素配合物23对二甲基硫醚,4-甲基吡啶,1-辛炔或甲氧基苯乙烯无反应性。在二甲基硫醚或4-甲基吡啶存在下,配合物5迅速取代了叶立德配体。两者合计,我们没有证据表明这些sulf或吡啶鎓的α-氧代羰基化合物可能表现为α-氧代卡宾替代物。
更新日期:2020-03-24
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