Discrimination of Octahedral versus Trigonal Bipyramidal Coordination Geometries of Homogeneous TiIV, VV, and MoVI Amino Triphenolate Complexes through Nitroxyl Radical Units

被引：13

作者：

Badetti, Elena ^{[1
,2
]}

Lloveras, Vega ^{[3
,4
]}

Romano, Francesco ^{[1
,2
]}

Di Lorenzo, Rosalia ^{[1
,2
]}

Veciana, Jaume ^{[3
,4
]}

Vidal-Gancedo, Jose ^{[3
,4
]}

Zonta, Cristiano ^{[1
,2
]}

Licini, Giulia ^{[1
,2
]}

机构：

[1] Univ Padua, Dipartimento Sci Chim, Via Marzolo 1, I-35131 Padua, Italy

[2] Univ Padua, CIRCC, Via Marzolo 1, I-35131 Padua, Italy

[3] Inst Ciencia Mat Barcelona CSIC, Campus Univ Bellaterra, Cerdanyola Del Valles 08193, Spain

[4] Networking Res Ctr Bioengn Biomat & & Nanomed CIB, Campus Univ Bellaterra, Cerdanyola Del Valles 08193, Spain

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2016年 / 31期

关键词：

Vanadium; Molybdenum; Titanium; Radicals; EPR spectroscopy; TRIS(PHENOLATE) COMPLEXES; VANADIUM(V); CATALYSIS; LIGANDS;

D O I：

10.1002/ejic.201600649

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A new stable radical-containing ligand and the corresponding V-V, Ti-IV, and Mo-VI complexes have been synthesized and studied by electron paramagnetic resonance (EPR) spectroscopy. To achieve this goal, a novel strategy for the post-derivatization of a triphenolamine (TPA) ligand has been developed. This has allowed the effective embedding of three TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) radicals in the corresponding metal complexes. In these systems, dipolar interactions among the organic radicals are strongly dependent on the geometry assumed in solution: a vertical bar Delta m(s)vertical bar = 2 transition is observed when the geometry of the complexes is octahedral, whereas no signal is detected with trigonal bipyramidal geometries.

引用

页码：4968 / 4973

页数：6

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