Revealing the Structure of Transition Metal Complexes of Formaldoxime

被引:5
|
作者
Golovanov, Ivan S. [1 ]
Malykhin, Roman S. [1 ]
Lesnikov, Vladislav K. [1 ]
Nelyubina, Yulia, V [2 ]
Novikov, Valentin V. [2 ]
Frolov, Kirill, V [3 ]
Stadnichenko, Andrey, I [4 ]
Tretyakov, Evgeny, V [1 ]
Ioffe, Sema L. [1 ]
Sukhorukov, Alexey Yu [1 ,5 ]
机构
[1] Russian Acad Sci, ND Zelinsky Inst Organ Chem, Moscow 119991, Russia
[2] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Moscow 119991, Russia
[3] Russian Acad Sci, Shubnikov Inst Crystallog FSRC Crystallog & Photo, Moscow 119991, Russia
[4] Russian Acad Sci, Siberian Branch, Boreskov Inst Catalysis, Novosibirsk 630090, Russia
[5] Plekhanov Russian Univ Econ, Moscow 117997, Russia
基金
俄罗斯基础研究基金会;
关键词
KOMPLEXSALZE DES FORMALDOXIMS; COORDINATION-COMPOUNDS; AEROBIC OXIDATION; DESFERRIOXAMINE-B; CRYSTAL-STRUCTURE; NICKEL(IV) COMPLEXES; FORMALDEHYDE OXIME; AQUEOUS-SOLUTION; IRON COMPLEXES; MANGANESE;
D O I
10.1021/acs.inorgchem.0c03362
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Aerobic reactions of iron(III), nickel(II), and manganese(II) chlorides with formaldoxime cyclotrimer (tfoH(3)) and 1,4,7-triazacyclononane (tacn) produce indefinitely stable complexes of general formula [M(tacn)(tfo)]Cl. Although the formation of formaldoxime complexes has been known since the end of 19th century and applied in spectrophotometric determination of D-metals (formaldoxime method), the structure of these coordination compounds remained elusive until now. According to the X-ray analysis, [M(tacn)(tfo)](+) cation has a distorted adamantane-like structure with the metal ion being coordinated by three oxygen atoms of deprotonated tfoH(3) ligand. The metal has a formal +4 oxidation state, which is atypical for organic complexes of iron and nickel. Electronic structure of [M(tacn)(tfo)]+ cations was studied by XPS, NMR, cyclic (CV) and differential pulse (DPV) voltammetries, Mossbauer spectroscopy, and DFT calculations. Unusual stabilization of high-valent metal ion by tfo(3-) ligand was explained by the donation of electron density from the nitrogen atom to the antibonding orbital of the metal-oxygen bond via hyperconjugation as confirmed by the NBO analysis. All complexes [M(tacn)(tfo)]Cl exhibited high catalytic activity in the aerobic dehydrogenative dimerization of p-thiocresol under ambient conditions.
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页码:5523 / 5537
页数:15
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