Weber Dieter, Gagné Michel R
Caudill Laboratories, Department of Chemistry, University of North Carolina at Chapel Hill, NC 27599, USA.
Chem Sci. 2013;47(1):335-338. doi: 10.1039/C2SC21281A.
While investigating the gold(i)-catalyzed intramolecular hydroarylation of allenes, the structure of a digoldvinyl intermediate was verified. Instead of the previously proposed geminally diaurated binding mode for the digold when L = PPh, an alternative σ-π-diauration mode was observed with the bulkier ligand L = P(-Tol). Reactivity studies indicate the σ-π-mode has a disproportionate effect on protonolysis reactivity.
在研究金（I）催化的丙二烯分子内氢芳基化反应时，二金乙烯基中间体的结构得到了验证。当L = PPh时，对于二金配合物，未观察到先前提出的偕二金配位模式，而是与体积更大的配体L = P（-Tol）观察到了另一种σ-π-二金配位模式。反应活性研究表明，σ-π模式对质子解反应活性有不成比例的影响。
