SYNTHESIS AND STRUCTURE OF PALLADACYCLOPENTADIENYL COMPLEX WITH ACENAPHTHENE-1,2-DIIMINE LIGAND

• Published in: Journal of structural chemistry 2022-08, Vol.63 (8), p.1304-1312
• Main Authors: Romashev, N. F., Bakaev, I. V., Komlyagina, V. I., Sokolov, M. N., Gushchin, A. L.
• Format: Article
• Language: English
• Subjects: Acetonitrile; Anions; Atomic; Atomic/Molecular Structure and Spectra; Carbon; Chemistry; Chemistry and Materials Science; Crystal structure; Crystals; Density functional theory; Dimethyl ether; Electronic structure; Inorganic Chemistry; Molecular; Nitrogen atoms; Optical and Plasma Physics; Oxidation; Palladium; Physical Chemistry; Reduction; Single crystals; Solid State Physics; Unit cell
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1134/S002247662208011X

The organometallic complex [Pd(dpp-bian)(C 4 (COOMe) 4 )]·(C 2 H 5 ) 2 O ( 1 ·(C 2 H 5 ) 2 O) is obtained by the interaction of [Pd 2 (dba) 3 ] (dba = dibenzylideneacetone) with dimethyl ether of acetylenedicarboxylic acid and 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) in the 1:4:2 molar ratio. During the oxidative addition reaction the 1,2,3,4-tetrakis(methoxycarbonyl)buta-1,3-dienyl dianion is formed from two molecules of dimethyl ether of acetylenedicarboxylic acid. This dianion is coordinated to palladium(II) via 1 and 4 carbon atoms with the formation of the palladacyclopentadienyl moiety. The crystal structure is determined by the single crystal X-ray diffraction analysis. The 1 ·(C 2 H 5 ) 2 O compound crystallizes in the orthorhombic crystal system ( Pbca ) with unit cell parameters a  = 16.9069(3) Å, b  = 23.5618(6) Å, c  = 23.8902(7) Å, V  = 9516.83(40) Å 3 . Each palladium atom has an almost square planar environment composed of two dpp-bian nitrogen atoms and two carbon atoms of the (C 4 (COOMe) 4 ) 2– anion. The cyclic voltammogram of 1 in acetonitrile reveals irreversible oxidation at E a  = 1.43 V, reversible reduction at E 1/2  = 0.62 V, and irreversible reduction at E b = 1.52 V. The electronic structure of complex 1 is studied within the density functional theory.