Dhara Debabrata, Scheschkewitz David, Chandrasekhar Vadapalli, Yildiz Cem B, Jana Anukul
Tata Institute of Fundamental Research Hyderabad, Gopanpally, Hyderabad-500046, Telangana, India.
Krupp-Chair of General and Inorganic Chemistry, Saarland University, 66123 Saarbrücken, Germany.
Chem Commun (Camb). 2021 Jan 26;57(6):809-812. doi: 10.1039/d0cc05461e.
We report the reactivity of isolable Au(i)-hydride stabilized by an NHC-coordinated diphosphene towards substrates containing C-C and N-N multiple bonds (NHC = N-heterocyclcic carbene). Reactions with dimethyl acetylenedicarboxylate and azobenzene lead to a trans-addition of the Au(i)-H across the C-C triple bond and the N-N double bond, respectively. In contrast, the reaction with ethyl diazoacetate affords a gold(i)-hydrazonide as the 1,1-addition product to the terminal nitrogen atom. With phenyl acetylene, the corresponding Au(i)-alkynyl complex is obtained under the elimination of dihydrogen. Strikingly, diphosphene-containing Au(i)-hydride is more reactive - affording different products in some cases - than a related NHC-stabilized Au(i)-hydride without the mediating diphosphene moiety.
我们报道了一种由NHC配位的二膦稳定的可分离的金（I）-氢化物对含有碳-碳和氮-氮多重键的底物的反应活性（NHC = N-杂环卡宾）。与乙酰基二甲基二羧酸酯和偶氮苯的反应分别导致金（I）-氢在碳-碳三键和氮-氮双键上的反式加成。相比之下，与重氮乙酸乙酯的反应产生一种金（I）-酰肼作为在末端氮原子上的1,1-加成产物。与苯乙炔反应时，在消除氢气的情况下得到相应的金（I）-炔基配合物。引人注目的是，含二膦的金（I）-氢化物比没有介导二膦部分的相关NHC稳定的金（I）-氢化物更具反应活性——在某些情况下会产生不同的产物。
