Gold(I) Heteroatom-Substituted Imido Complexes. Amino Nitrene Loss from [(LAu)<sub>3</sub>(μ-NNR<sub>2</sub>)]<sup>+</sup>
作者:Bruce W. Flint、Yi Yang、Paul R. Sharp
DOI:10.1021/ic990586u
日期:2000.2.1
The heteroatom-substituted imido complexes [(LAu)3(mu-NX)]+ (X = NR2, R = Ph, Me, Bz; X = OH, Cl; L = a phosphine) have been prepared from the reactions of NH2X with [(LAu)3(mu-O)]+. Thermally unstable [(LAu)3(mu-NNMe2)]+ (L = P(p-XC6H4)3, X = H, F, Me, Cl, MeO) decompose to the gold cluster [LAu]6(2+) and tetramethyltetrazene Me2NN=NNMe2. The decomposition is first-order overall with a rate constant
杂原子取代的亚氨基配合物[(LAu)3(mu-NX)] +(X = NR2,R = Ph,Me,Bz; X = OH,Cl; L = a膦)已由NH2X反应制备与[(LAu)3(mu-O)] +。热不稳定的[(LAu)3(mu-NNMe2)] +(L = P(p-XC6H4)3,X = H,F,Me,Cl,MeO)分解成金簇[LAu] 6(2+)和四甲基四烯Me2NN = NNMe2。总的来说,分解是一阶的,速率常数随膦配体的pKa的增加而增加。分解的活化参数为deltaH(不等于)= 99(4)kJ / mol和deltaS(不等于)= 18.5(5)L / PPh3和deltaH(不等于)= 78的J / K.mol (3)对于L = P(p-MeOC6H4)3,kJ / mol和deltaS(不等于)= -47(2)J / K.mol。类似的[(LAu)3(mu-NNBz2)] +的