Bruckhoff Tim, Ballmann Joachim, Gade Lutz H
Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 276, 69120, Heidelberg, Germany.
Angew Chem Int Ed Engl. 2024 May 6;63(19):e202320064. doi: 10.1002/anie.202320064. Epub 2024 Apr 4.
A mononuclear, T-shaped palladium(I) d metalloradical (3), stabilized by a bulky carbazole-based PNP-ligand, was obtained by reduction of palladium chloride or thermal Pd-C bond homolysis of the corresponding neopentyl complex. Pressurizing with CO gave the Pd(I) carbonyl complex, which was structurally characterized by X-ray diffraction. Delocalization of the unpaired electron to the carbonyl carbon was detected by EPR spectroscopy and theoretically modeled by DFT and ab initio methods. The partially reduced and radicalized CO slowly reacts with di(tert-butyl) disulfide under homolytic S-S cleavage and C-S bond formation to give the corresponding metallathioester.
通过还原氯化钯或相应新戊基配合物的热钯-碳键均裂反应，得到了一种由庞大的咔唑基PNP配体稳定的单核、T形钯（I）金属自由基（3）。用一氧化碳加压得到钯（I）羰基配合物，通过X射线衍射对其结构进行了表征。通过电子顺磁共振光谱检测到未成对电子离域到羰基碳上，并通过密度泛函理论和从头算方法进行了理论模拟。部分还原和自由基化的一氧化碳在均裂S-S键断裂和C-S键形成的情况下与二叔丁基二硫化物缓慢反应，生成相应的金属硫酯。
