Synthesis and Characterization of (smif)2Mn (n=0, M = V, Cr, Mn, Fe, Co, Ni, Ru; n =+1, M = Cr, Mn, Co, Rh, Ir; smif=1,3-di-(2-pyridyl)-2-azaallyl)
Synthesis and Characterization of (smif)2Mn (n=0, M = V, Cr, Mn, Fe, Co, Ni, Ru; n =+1, M = Cr, Mn, Co, Rh, Ir; smif=1,3-di-(2-pyridyl)-2-azaallyl)
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DOI：
10.1021/ic200376f
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发表时间：
2011-12-19
影响因子：
4.6
通讯作者：
Cundari, Thomas R.
中科院分区：
文献类型：
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作者：
Frazier, Brenda A.;Bartholomew, Erika R.;Cundari, Thomas R.
合成了一系列以三齿配体Smif（1，3-二（2-吡啶基）-2-氮杂烯丙基）为特征的Werner配合物。（smif）（2）M（1-M; M = Cr，Fe）的合成通过用2当量的（smif）H（1，3-二-（2-吡啶基）-2-氮杂丙烯）处理M（NSiMe 3）（2）（THF）（n）（M = Cr，n = 2; Fe，n = 1）完成;邻甲基化的（（o）Mesmif）（2）Fe（2-Fe）和（（o）Me（2）smif）（2）Fe（3-Fe）类似地制备。MX2变体与2当量的Li（smif）或Na（smif）的置换生成1-M（M = Cr、Mn、Fe、Co、Ni、Zn、Ru）。VCl_3（THF）（3）与2Li（smif）在还原当量Na/Hg存在下进行复分解反应，得到1-V，而2Na（smif）与IrCl_3（THF）_3在NaBPh_4存在下进行复分解反应，得到[（smif）（2）Ir] BPh_4（1（+）-Ir）。电化学实验导致1-M（M = Cr，Mn，Co）被AgOTf氧化生成[（smif）（2）M]OTf（1（+）-M），Rh-2（O2 CCF 3）（4）用4当量Na（smif）和2 AgOTf处理生成1（+）-Rh。通过核磁共振、电子顺磁共振、紫外-可见光谱、超导量子干涉仪、X射线晶体学和密度泛函理论计算对化合物进行了表征。配体内（IL）跃迁来自于电子从smif骨架的独特CNCnb（非键合）轨道到配体pi*-型轨道的促进作用，是强烈的（约10 000-60 000 M（-1）cm（-1）），在紫外-可见光谱中占主导地位，并使晶体具有金属外观。高能K边谱表明1-Cr中的smif是氧化还原非无辜的，其电子构型最好描述为（smif（-））（smif（2-））Cr（III）;获得了1-Cr的不寻常的S = 1 EPR谱（X带）。
A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe3)(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX2 variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl3(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl3(THF)3 in the presence of NaBPh4 gave [(smif)(2)Ir]BPh4 (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh-2(O2CCF3)(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNCnb (nonbonding) orbitals of the smif backbone to ligand pi*-type orbitals are intense (epsilon approximate to 10 000-60 000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr.