TY - JOUR

T1 - Synthesis and structure of palladacyclopentadienyl complex with acenaphthene-1,2-diimine ligand

AU - Romashev, N. F.

AU - Bakaev, I. V.

AU - Komlyagina, V. I.

AU - Sokolov, M. N.

AU - Gushchin, A. L.

N1 - Funding Information: The work was supported by RFBR (grant No. 21-13-00092) and the Ministry of Sciences and Higher Education of the Russian Federation (project No. 121031700315-2). Publisher Copyright: © 2022, Pleiades Publishing, Ltd.

PY - 2022/8

Y1 - 2022/8

N2 - The organometallic complex [Pd(dpp-bian)(C4(COOMe)4)]·(C2H5)2O (1·(C2H5)2O) is obtained by the interaction of [Pd2(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·(C2H5)2O 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) Å3. Each palladium atom has an almost square planar environment composed of two dpp-bian nitrogen atoms and two carbon atoms of the (C4(COOMe)4)2– anion. The cyclic voltammogram of 1 in acetonitrile reveals irreversible oxidation at Ea = 1.43 V, reversible reduction at E1/2 = 0.62 V, and irreversible reduction at Eb = 1.52 V. The electronic structure of complex 1 is studied within the density functional theory.

AB - The organometallic complex [Pd(dpp-bian)(C4(COOMe)4)]·(C2H5)2O (1·(C2H5)2O) is obtained by the interaction of [Pd2(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·(C2H5)2O 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) Å3. Each palladium atom has an almost square planar environment composed of two dpp-bian nitrogen atoms and two carbon atoms of the (C4(COOMe)4)2– anion. The cyclic voltammogram of 1 in acetonitrile reveals irreversible oxidation at Ea = 1.43 V, reversible reduction at E1/2 = 0.62 V, and irreversible reduction at Eb = 1.52 V. The electronic structure of complex 1 is studied within the density functional theory.

KW - acenaphthene-1,2-diimine

KW - cyclic voltammetry

KW - DFT calculations

KW - palladacyclopentadiene

KW - palladium

KW - single crystal XRD

UR - http://www.scopus.com/inward/record.url?scp=85137475091&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/9544649d-c316-3c9f-bd7c-19db9bd3e3e7/

U2 - 10.1134/S002247662208011X

DO - 10.1134/S002247662208011X

M3 - Article

AN - SCOPUS:85137475091

VL - 63

SP - 1304

EP - 1312

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 8

ER -