TY - JOUR
T1 - Octahedral bis(2-thenoyltrifluoroacetonato)-ethylenediamine Co(II), Ni(II) and Cu(II) complexes
T2 - Synthetic, structural, electrochemical, and theoretical studies
AU - Ahumada, Guillermo
AU - Roisnel, Thierry
AU - Kahlal, Samia
AU - Carrillo, David
AU - Córdova, Ricardo
AU - Saillard, Jean Yves
AU - Hamon, Jean René
AU - Manzur, Carolina
N1 - Funding Information:
Financial support from the Fondo Nacional de Desarrollo Cient?fico y Tecnol?gico [FONDECYT (Chile), grant no. 1140903 (C.M. and D.C.)], FONDEQUIP [EQM130154], the Vicerrector?a de Investigaci?n y Estudios Avanzados, Pontificia Universidad Cat?lica de Valpara?so, Chile (C.M. and D.C.), the CNRS and the Universit? de Rennes 1 is gratefully acknowledged. The GENCI-CINES and GENCI-IDRISS French national computer centers are acknowledged for computational resources (grant x2016-087367). This research has been performed as part of the Chilean-French International Associated Laboratory for ?Inorganic Functional Materials?? (LIA-CNRS N?836). G.A. thanks the CONICYT (Chile) for support of a graduate fellowship N?21120098.
Funding Information:
Financial support from the Fondo Nacional de Desarrollo Científico y Tecnológico [FONDECYT (Chile), grant no. 1140903 (C.M. and D.C.)], FONDEQUIP [EQM130154], the Vicerrectoría de Investigación y Estudios Avanzados , Pontificia Universidad Católica de Valparaíso , Chile (C.M. and D.C.), the CNRS and the Université de Rennes 1 is gratefully acknowledged. The GENCI-CINES and GENCI-IDRISS French national computer centers are acknowledged for computational resources (grant x2016-087367). This research has been performed as part of the Chilean-French International Associated Laboratory for “Inorganic Functional Materials’’ (LIA-CNRS N°836). G.A. thanks the CONICYT (Chile) for support of a graduate fellowship N° 21120098 .
Publisher Copyright:
© 2017 Elsevier B.V.
PY - 2018/1/30
Y1 - 2018/1/30
N2 - We report the synthesis of three new octahedral bis(2-thenoyltrifluoroacetonato)-ethylenediamine metal(II) complexes [M(TTA)2(en)] (M = Co, 2a; Ni, 2b; Cu, 2c) resulting from the coordination of the diamine onto the bis(β-diketonate) precursors [Co(TTA)2(CH3OH)2] (1a), [Ni(TTA)2(H2O)2] (1b) and [Cu(TTA)2] (1c), respectively. The six-coordinate paramagnetic complexes 2a-c have been isolated as neutral, air and thermally stable solids in high yields (>80%) and have been fully characterized by elemental analysis, ESI+ HRMS, FT-IR and UV–vis spectroscopy. Single-crystal X-ray diffraction studies indicate that the metal(II) ion sits in a pseudo-octahedral environment; the copper derivative 2c showing a significant elongation along the O–Cu–O axis due to Jahn-Teller distorsion associated with the “eg” electron occupation of the dz2-type MO. The three complexes 2a-c display similar cyclic voltammetric behavior exhibiting two irreversible anodic waves, tentatively assigned to the M(II)/M(III) redox couples and to the oxidation of soluble short oligomeric species generated during the first redox process, respectively. No deposits of polymeric species on the electrode surface occured. The electronic structures of 2a-c and their cations have been analysed through DFT calculations, allowing providing a consistent view of their structure and properties. TDDFT calculations have been used to interpret the major features of their UV–vis spectra.
AB - We report the synthesis of three new octahedral bis(2-thenoyltrifluoroacetonato)-ethylenediamine metal(II) complexes [M(TTA)2(en)] (M = Co, 2a; Ni, 2b; Cu, 2c) resulting from the coordination of the diamine onto the bis(β-diketonate) precursors [Co(TTA)2(CH3OH)2] (1a), [Ni(TTA)2(H2O)2] (1b) and [Cu(TTA)2] (1c), respectively. The six-coordinate paramagnetic complexes 2a-c have been isolated as neutral, air and thermally stable solids in high yields (>80%) and have been fully characterized by elemental analysis, ESI+ HRMS, FT-IR and UV–vis spectroscopy. Single-crystal X-ray diffraction studies indicate that the metal(II) ion sits in a pseudo-octahedral environment; the copper derivative 2c showing a significant elongation along the O–Cu–O axis due to Jahn-Teller distorsion associated with the “eg” electron occupation of the dz2-type MO. The three complexes 2a-c display similar cyclic voltammetric behavior exhibiting two irreversible anodic waves, tentatively assigned to the M(II)/M(III) redox couples and to the oxidation of soluble short oligomeric species generated during the first redox process, respectively. No deposits of polymeric species on the electrode surface occured. The electronic structures of 2a-c and their cations have been analysed through DFT calculations, allowing providing a consistent view of their structure and properties. TDDFT calculations have been used to interpret the major features of their UV–vis spectra.
KW - 2-Thenoyltrifluoroacetone
KW - Electrochemistry, DFT and TDDFT calculations
KW - Octahedral complexes
KW - Single crystal X-ray structure
UR - http://www.scopus.com/inward/record.url?scp=85018782660&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2017.04.050
DO - 10.1016/j.ica.2017.04.050
M3 - Article
AN - SCOPUS:85018782660
SN - 0020-1693
VL - 470
SP - 221
EP - 231
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -