TY - JOUR
T1 - Comparison of the structure and stability of new α-diimine complexes of copper(I) and silver(I): Density functional theory versus experimental
AU - Rosa, Vitor
AU - Santos, Carla I. M.
AU - Welter, Richard
AU - Aullón, Gabriel
AU - Lodeiro, Carlos
AU - Avilés, Teresa
N1 - We thank Fundacao para a Ciencia e Tecnologia, Portugal, for funding (Projects PTDC/QUI/66440/2006 and PTDC/QUI_QUI/099873/2008 and Portugal/France Cooperation Program "Programa Pessoa 2009-2010"). We also thank the Portuguese-Spanish Integrated Action 2008, No. E-77/08 (HP 2007-0040). Financial support for this work was also provided by the Spanish Direccion General de Investigacion through Grant CTQ2008-06670-C02-01/BQU and by the Departament d'Innovacio, Universitats i Empresa of Generalitat de Catalunya through Grant 2009SGR-1459. The computing resources at the Centre de Supercomputacio de Catalunya were made available in part through a grant of Fundacio Catalana per a la Recerca and Universitat de Barcelona. C.L. thanks the INCITE-Xunta de Galicia, Spain, for the "Isidro Parga Pondal" Research Program.
PY - 2010/10/4
Y1 - 2010/10/4
N2 - New compounds of the general formulas [M(Ar-BIAN)2]BF 4 and [M(Ar-BIAN)(NCMe)2]BF4, where M = Cu I or AgI and Ar-BIAN = bis(aryl) acenaphthenequinonediimine, were synthesized by the direct reaction of [Cu(NCMe)4]BF4 or [Ag(NCMe)4]BF4 with the corresponding Ar-BIAN ligand in dried CH2Cl2. The synthesized compounds are [M(o,ó,p-Me3C6H 2-BIAN)2]BF4 where M = CuI (1) and AgI (2), [M(o,ó-iPr2C6H 3-BIAN)(NCMe)2]BF4 where M = CuI (3) and AgI (4), and [Ag(o,ó-iPr2C6H 3-BIAN)2]BF4 (5). The crystal structures of compounds 1-3 and 5 were solved by single-crystal X-ray diffraction. In all cases copper(I) or silver(I) are in a distorted tetrahedron that is constructed from the four nitrogen atoms of the two α-diimine ligands or, in 3, from one α-diimine ligand and two acetonitrile molecules. All compounds were characterized by elemental analyses, matrix-assisted laser desorption-ionization time-of-flight mass spectrometry, and IR, UV-vis, and 1H NMR spectroscopy. The analysis of the molecular geometry and the energetic changes for the formation reactions of the complexes, in a CH2Cl2 solution, were evaluated by density functional theory calculations and compared with the experimental results.
AB - New compounds of the general formulas [M(Ar-BIAN)2]BF 4 and [M(Ar-BIAN)(NCMe)2]BF4, where M = Cu I or AgI and Ar-BIAN = bis(aryl) acenaphthenequinonediimine, were synthesized by the direct reaction of [Cu(NCMe)4]BF4 or [Ag(NCMe)4]BF4 with the corresponding Ar-BIAN ligand in dried CH2Cl2. The synthesized compounds are [M(o,ó,p-Me3C6H 2-BIAN)2]BF4 where M = CuI (1) and AgI (2), [M(o,ó-iPr2C6H 3-BIAN)(NCMe)2]BF4 where M = CuI (3) and AgI (4), and [Ag(o,ó-iPr2C6H 3-BIAN)2]BF4 (5). The crystal structures of compounds 1-3 and 5 were solved by single-crystal X-ray diffraction. In all cases copper(I) or silver(I) are in a distorted tetrahedron that is constructed from the four nitrogen atoms of the two α-diimine ligands or, in 3, from one α-diimine ligand and two acetonitrile molecules. All compounds were characterized by elemental analyses, matrix-assisted laser desorption-ionization time-of-flight mass spectrometry, and IR, UV-vis, and 1H NMR spectroscopy. The analysis of the molecular geometry and the energetic changes for the formation reactions of the complexes, in a CH2Cl2 solution, were evaluated by density functional theory calculations and compared with the experimental results.
UR - http://www.scopus.com/inward/record.url?scp=77957267618&partnerID=8YFLogxK
U2 - 10.1021/ic100450y
DO - 10.1021/ic100450y
M3 - Article
C2 - 20812753
AN - SCOPUS:77957267618
SN - 0020-1669
VL - 49
SP - 8699
EP - 8708
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 19
ER -