Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel

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• 作者：Laura J. Clouston ; Varinia Bernales ; Ryan C. Cammarota ; Rebecca K. Carlson ; Eckhard Bill ; Laura Gagliardi ; Connie C. Lu
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 21, 2015
• 年：2015
• 卷：54
• 期：24
• 页码：11669-11679
• 全文大小：527K
• ISSN：1520-510X

文摘

Zero-valent iron, cobalt, and nickel were installed into the metalloligand V[N(o-(NCH₂P(ⁱPr)₂)C₆H₄)₃] (1, VL), generating the heterobimetallic trio FeVL (2), CoVL (3), and NiVL (4), respectively. In addition, the one-electron-oxidized analogues [FeVL]X ([2^ox]X, where X^{鈥?/sup> = BPh₄ or PF₆) and [CoVL]BPh₄ ([3ox]BPh₄) were prepared. The complexes were characterized by a host of physical methods, including cyclic voltammetry, X-ray crystallography, magnetic susceptibility, electronic absorption, NMR, electron paramagnetic resonance (EPR), and M枚ssbauer spectroscopies. The CoV and FeV heterobimetallic compounds have short M鈥揤 bond lengths that are consistent with M鈥揗 multiple bonding. As revealed by theoretical calculations, the M鈥揤 bond is triple in 2, 2ox, and 3ox, double in 3, and dative (Ni 鈫?V) in 4. The (d鈥揹)10 species, 2 and 3ox, are diamagnetic and exhibit large diamagnetic anisotropies of 鈭?700 脳 10鈥?6 m3/molecule. Complexes 2 and 3ox are also characterized by intense visible bands at 760 and 610 nm (蔚 > 1000 M鈥? cm鈥?), respectively, which correspond to an intermetal (M 鈫?V) charge-transfer transition. Magnetic susceptibility measurements and EPR characterization establish S = 1/₂ ground states for (d鈥揹)9 2ox and (d鈥揹)11 3, while (d鈥揹)12 4 is S = 1 based on Evans鈥?method.}