131063-11-1Relevant articles and documents
Novel vanadium complexes supported by a bulky tris(pyrazolyl)borate ligand
Petrov, Pavel A.,Smolentsev, Anton I.,Bogomyakov, Artem S.,Konchenko, Sergey N.
, p. 60 - 64 (2017)
The V(III) complex [V(TptBu2)Cl2] (1, TptBu2?=?hydrotris(3,5-di-tert-butylpyrazolyl)borate) was synthesized by the reaction of [VCl3(THF)3] (prepared in situ) and K(TptBu2). Reduction of 1 with potassium mirror afforded the V(II) complex [V(TptBu2)Cl] (2). Both complexes were characterized by means of a single crystal X-ray diffraction. 1 represents the first example of pentacoordinated vanadium tris(pyrazolyl)borate (Tp) complexes. The V(III) ion environment is a distorted trigonal bipyramid. 2 is the first V(II) Tp-complex. The V(II) ion has tetrahedral environment, and the Cl atom is deviated from the B–V axis (∠B(1)–V(1)–Cl(1)?=?157.8°). Magnetic susceptibility measurements showed reasonable μeff values at 300?K: 2.80 (1) and 3.78 (2) μB, those prove the oxidation states of V: +3 (1) and +2 (2).
Non-Oxido-Vanadium(IV) Metalloradical Complexes with Bidentate 1,2-Dithienylethene Ligands: Observation of Reversible Cyclization of the Ligand Scaffold in Solution
Fugel, Malte,Grabowsky, Simon,Harmer, Jeffrey R.,Kleemiss, Florian,Lork, Enno,Schlüter, Dirk,Sugimoto, Kunihisa,Vogt, Matthias
, p. 1335 - 1343 (2020)
Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2Cl2] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P). This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P). Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution.
Reductive transformation of V(iii) precursors into vanadium(ii) oxide nanowires
Ojelere, Olusola,Graf, David,Ludwig, Tim,Vogt, Nicholas,Klein, Axel,Mathur, Sanjay
, p. 6842 - 6849 (2018/06/01)
Vanadium(ii) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium(iii) complexes with bi-dentate O,N-chelating heteroarylalkenol ligands (DmoxCHCOCF3, PyCHCOCF3 and PyNCOCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. The chemical identity of V(iii) complexes and their redox behaviour were unambiguously established by single crystal X-ray diffraction studies, cyclic voltammetry, spectrometric studies and DFT calculations. Transformation into the metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures, respectively.