Isolation and Characterization of Heteroleptic Mononuclear Palladium(I) Complexes
Isolation and Characterization of Heteroleptic Mononuclear Palladium(I) Complexes
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DOI：
10.1021/jacs.2c08765
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发表时间：
2022-10-18
影响因子：
15
通讯作者：
Mirica, Liviu M.
中科院分区：
文献类型：
--
作者：
Tran, Giang N.;Bouley, Bailey S.;Mirica, Liviu M.
涉及Pd（0）/Pd（II）催化循环的催化转化是非常公知的，并且涉及高价Pd（III）和Pd（IV）以及低价Pd（I）中间体的方法近年来也引起了兴趣。虽然在这些催化循环中提出了低价Pd（I）中间体，但分离和表征的单核Pd（I）物种非常罕见。在此，我们报告了两个heteroleptic单核Pd（I）配合物的分离稳定的thiothiapyridinophane配体，充分其特征在于单晶X-射线衍射，EPR，IR，紫外-可见光谱;和计算研究。令人兴奋的是，这些Pd（I）络合物之一显示Kumada Csp（3）-Csp（2）交叉偶联能力，并且对另一个的初步研究显示了Csp（3）-H键活化的直接证据，提出在Pd（I）中心发生。
Catalytic transformations involving Pd(0)/Pd(II) catalytic cycles are very well known, and processes involving high-valent Pd(III) and Pd(IV) and low-valent Pd(I) intermediates have also gained interest in recent years. Although low-valent Pd(I) intermediates are proposed in these catalytic cycles, isolated and characterized mononuclear Pd(I) species are very rare. Herein, we report the isolation of two heteroleptic mononuclear Pd(I) complexes stabilized by dithiapyridinophane ligands that were fully characterized by single-crystal X-ray diffraction; EPR, IR, UV-vis spectroscopies; and computational studies. Excitingly, one of these Pd(I) complexes shows Kumada Csp(3)-Csp(2) cross-coupling competency, and initial studies of the other shows direct evidence for Csp(3)-H bond activation proposed to occur at the Pd(I) center.