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
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
收藏
页码:4968 / 4973
页数:6
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