Ligand Reorganization in the Coordination Sphere of a CCC-NHC Pincer Fe Complex and Transient Absorption Spectroscopic Characterization of [( Bu C i C i C Bu ) 2 Fe]I
Ligand Reorganization in the Coordination Sphere of a CCC-NHC Pincer Fe Complex and Transient Absorption Spectroscopic Characterization of [( Bu C i C i C Bu ) 2 Fe]I
复制标题
CCC-NHC Pincer Fe 配合物配位域中的配体重组和 [( Bu C i C i C Bu ) 2 Fe]I 的瞬态吸收光谱表征
DOI：
10.1021/acs.organomet.3c00386
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发表时间：
2024
期刊：
影响因子：
2.8
通讯作者：
Hollis, T. Keith
中科院分区：
文献类型：
--
作者：
Mensah, Joshua;Adiraju, Venkata K.;Cope, James D.;Lamb, Robert W.;Li, Xiao X.;Donnadieu, Bruno;Rubtsov, Igor V.;Webster, Charles Edwin;Hollis, T. Keith
通过Zr金属化/金属转移路线合成了具有正丁基取代基的单配位和双配位CCC-NHC钳形Fe配合物。从分离的（BuCiCiCBu）ZrNMe 2Cl 2，3的直接金属化/金属转移和金属转移两者产生八面体配位的Fe（III）双配位络合物[（BuCiCiCBu）2Fe] Cl，2a。在过量的TMSCl和1当量的Fe源存在下，从原位分离的（BuCiCiCBu）ZrCl 3，5的金属转移产生单配体（BuCiCiCBu）FeCl 2，4。通过~ 1H NMR、紫外-可见光谱、飞秒瞬态吸收光谱、TD-DFT计算、沿着的质谱和X-射线单晶结构的测定，确定了[（BuCiCiCBu）_2Fe]~+，2转变为（BuCiCiCBu）FeCl_（2，4）配合物的条件。
Monoligated and bis-ligated CCC-NHC pincer Fe complexes withn-butyl substituents have been synthesized by the Zr metalation/transmetalation route. Both the direct metalation/transmetalation and transmetalation from the isolated (BuCiCiCBu)ZrNMe2Cl2,3,yielded the octahedrally coordinated Fe(III) bis-ligated complex [(BuCiCiCBu)2Fe]Cl,2a. Transmetalation fromin situand isolated (BuCiCiCBu)ZrCl3,5, in the presence of excess TMSCl and 1 equiv of the Fe source yielded the monoligated (BuCiCiCBu)FeCl2,4. Conditions that convert [(BuCiCiCBu)2Fe]+,2, to (BuCiCiCBu)FeCl2,4, complex have been found. Characterization included1H NMR, UV–visible, femtosecond transient absorption spectroscopies, TD-DFT computations, and mass spectroscopy along with X-ray crystallographic structure determinations.