Shivaraam R A Keerthi, Rajeshkumar Thayalan, Scopelliti Rosario, Z Ivković Ivica, Maron Laurent, Mazzanti Marinella
Group of Coordination Chemistry, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.
Laboratoire de Physique et Chimie des Nano-objets, Institut National des Sciences Appliquées, 31077, Toulouse, Cedex 4, France.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202414051. doi: 10.1002/anie.202414051. Epub 2024 Nov 9.
The dinitrogen (N) chemistry of lanthanides remains less developed compared to the d-block metals and lanthanide-promoted N functionalization chemistry in well-defined lanthanide complexes remains elusive. Here we report the synthesis and characterization (SQUID, EPR, DFT, X-Ray) of the siloxide supported heterobimetallic (Tm/K) complexes [{KTm(OSi(OBu))}(μ-η : η-N)] (1) and [K{Tm(OSi(OBu))}(μ-η : η-N)] (2). Complex 2 provides a rare example of a metal complex of the triply reduced N radical. The structure of 2 differs from the few previously reported N complexes as it presents two Tm and three K cations binding the N radical, facilitating N functionalization. Notably, the KTm-bound N moiety reacts with excess H to form NHCl in 18 % yield, and with MeOTf at room temperature to yield the dimethyl hydrazido complex [K{Tm(OSi(OBu))}(μ-(CH)NN(CH))] (3). Protonolysis of 3 yields MeHN-NMeH ⋅ 2HCl in 18 % yield.
与d区金属相比,镧系元素的二氮(N)化学发展程度较低,并且在定义明确的镧系配合物中镧系元素促进的N官能团化化学仍然难以捉摸。在此,我们报告了硅氧基支持的异双金属(Tm/K)配合物[{KTm(OSi(OBu))}(μ-η : η-N)] (1) 和 [K{Tm(OSi(OBu))}(μ-η : η-N)] (2) 的合成与表征(SQUID、EPR、DFT、X射线)。配合物2提供了一个罕见的三重还原N自由基金属配合物的例子。2的结构与之前报道的少数N配合物不同,因为它呈现出两个Tm和三个K阳离子与N自由基结合,促进了N官能团化。值得注意的是,KTm结合的N部分与过量的H反应,以18%的产率形成NHCl,并在室温下与MeOTf反应,生成二甲基肼基配合物[K{Tm(OSi(OBu))}(μ-(CH)NN(CH))] (3)。3的质子解反应以18%的产率生成MeHN-NMeH ⋅ 2HCl。