TY - JOUR
T1 - A new bis(1-naphthylimino)acenaphthene compound and its Pd(II) and Zn(II) complexes: Synthesis, characterization, solid-state structures and density functional theory studies on the syn and anti isomers
AU - Rosa, Vitor
AU - Avilés, Teresa
AU - Aullon, Gabriel
AU - Covelo, Berta
AU - Lodeiro, Carlos
N1 - We thank Fundacao para a Ciencia e Tecnologia, Portugal, for funding (Projects PTDC/QUI/66440/2006, PTDC/QUI/66250/2006) and for a doctoral fellowship to V.R.'(SFRH/BD/13777/2003). We also thank the Portuguese-Spanish Integrated Action-2008, No. E-77/08. Financial support for this work was also provided by the Spanish Direccion General de Investigacion (DGI) through Grant CTQ2005-08123-CO2-02/BQU and by the Departament d'Universitats, Recerca i Societat de la Informacio (DURSI) of Generalitat de Catalunya through Grant 2005SGR-0036. The computing resources at the Centre de Supercomputacio de Catalunya (CESCA) were made available in part through a grant of Fundacio Catalana per a la Recerca (FCR) and Universitat de Barcelona.
PY - 2008/9/1
Y1 - 2008/9/1
N2 - A new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, L1, and its Zn(II) and Pd(II) complexes [ZnCl2(L1)], 1, and [PdCl 2(L1)], 2, were synthesized. L1 was prepared by the "template method", reacting 1-naphthyl amine and acenaphthenequinone in the presence of ZnCl2, giving 1, which was further demetallated. Reaction of 1-naphthyl amine with acenaphthenequinone and PdCl2 afforded dichloride bis(1-naphthyl)acenaphthenequinonediimine palladium, 2. L1, 1, and 2 were obtained as a mixture of syn and anti isomers. Compound 2 was also obtained by the reaction of PdCl2 activated by refluxing it in acetonitrile followed by the addition of L1; by this route also a mixture of syn and anti isomers was obtained, but at a different rate. The solid-state structures of L1 and the anti isomer of compound 2 have been determined by single-crystal X-ray diffraction. All compounds have been characterized by elemental analyses; matrix-assisted laser desorption ionization-time-of-flight-mass spectrometry; IR; UV-vis; 1H, 13C, and 1H-1H correlation spectroscopy; 1H-13C heteronuclear single quantum coherence; 1H-13C heteronuclear single quantum coherence-total correlation spectroscopy; and 1H-1H nuclear Overhauser effect spectrometry NMR spectroscopies when applied. Density functional theory studies showed that both conformers for [PdCl 2(BIAN)] are isoenergetic, and they can both be obtained experimentally. However, we can predict that the isomerization process is not available in a square-planar complex, but it is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected.
AB - A new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, L1, and its Zn(II) and Pd(II) complexes [ZnCl2(L1)], 1, and [PdCl 2(L1)], 2, were synthesized. L1 was prepared by the "template method", reacting 1-naphthyl amine and acenaphthenequinone in the presence of ZnCl2, giving 1, which was further demetallated. Reaction of 1-naphthyl amine with acenaphthenequinone and PdCl2 afforded dichloride bis(1-naphthyl)acenaphthenequinonediimine palladium, 2. L1, 1, and 2 were obtained as a mixture of syn and anti isomers. Compound 2 was also obtained by the reaction of PdCl2 activated by refluxing it in acetonitrile followed by the addition of L1; by this route also a mixture of syn and anti isomers was obtained, but at a different rate. The solid-state structures of L1 and the anti isomer of compound 2 have been determined by single-crystal X-ray diffraction. All compounds have been characterized by elemental analyses; matrix-assisted laser desorption ionization-time-of-flight-mass spectrometry; IR; UV-vis; 1H, 13C, and 1H-1H correlation spectroscopy; 1H-13C heteronuclear single quantum coherence; 1H-13C heteronuclear single quantum coherence-total correlation spectroscopy; and 1H-1H nuclear Overhauser effect spectrometry NMR spectroscopies when applied. Density functional theory studies showed that both conformers for [PdCl 2(BIAN)] are isoenergetic, and they can both be obtained experimentally. However, we can predict that the isomerization process is not available in a square-planar complex, but it is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected.
UR - http://www.scopus.com/inward/record.url?scp=51849084229&partnerID=8YFLogxK
U2 - 10.1021/ic800790u
DO - 10.1021/ic800790u
M3 - Article
C2 - 18671386
AN - SCOPUS:51849084229
SN - 0020-1669
VL - 47
SP - 7734
EP - 7744
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 17
ER -