A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour

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A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour. / Romashev, Nikolai F.; Gushchin, Artem L.; Fomenko, Iakov S. et al.

In: Polyhedron, Vol. 173, 114110, 15.11.2019.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{1205e56e9f654624a6084c61a9e55a75,

title = "A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour",

abstract = "Reaction of [{Rh(COD)}2(μ-Cl)2] with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) has afforded a new organometallic complex [Rh(COD)(dpp-bian)Cl] (1). The crystal structure of 1·0.25H2O was determined by X-ray single crystal analysis. The rhodium(I) ion has a distorted square-pyramidal coordination. The Rh[sbnd]Cl distance (2.5908 (12) {\AA}) is rather long, indicating weak coordination of the chloride. Dissociation of chloride in solution to produce cationic [Rh(COD)(bian)]+ ([1-Cl]+) was confirmed by ESI-MS, 1H NMR, CV and DFT calculations. Cyclic voltammetry of 1 in acetonitrile (CH3CN) showed two reversible one-electron redox waves at E1/2 = −0.36 V and −1.18 V (versus Ag/AgCl) attributable to successive reduction of the dpp-bian ligand in [1-Cl]+. DFT calculations were performed to explain the anomalously long Rh[sbnd]Cl distance and interpret the reduction sequence of 1.",

keywords = "Acenaphthene-1,2-diimines, Cyclic voltammetry, DFT calculations, Rhodium, Synthesis, Acenaphthene-1, 2-diimines, HYDROGENATION, DIIMINE NI(II) CATALYST, REACTIVITY, CRYSTAL-STRUCTURES, POLYMERIZATION, REDUCTION, SPECTROSCOPY, X-RAY, VALENCE TAUTOMERISM, METAL",

author = "Romashev, {Nikolai F.} and Gushchin, {Artem L.} and Fomenko, {Iakov S.} and Abramov, {Pavel A.} and Mirzaeva, {Irina V.} and Kompan'kov, {Nikolay B.} and Kal'nyi, {Danila B.} and Sokolov, {Maxim N.}",

year = "2019",

month = nov,

day = "15",

doi = "10.1016/j.poly.2019.114110",

language = "English",

volume = "173",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - A new organometallic rhodium(I) complex with dpp-bian ligand: Synthesis, structure and redox behaviour

AU - Romashev, Nikolai F.

AU - Gushchin, Artem L.

AU - Fomenko, Iakov S.

AU - Abramov, Pavel A.

AU - Mirzaeva, Irina V.

AU - Kompan'kov, Nikolay B.

AU - Kal'nyi, Danila B.

AU - Sokolov, Maxim N.

PY - 2019/11/15

Y1 - 2019/11/15

N2 - Reaction of [{Rh(COD)}2(μ-Cl)2] with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) has afforded a new organometallic complex [Rh(COD)(dpp-bian)Cl] (1). The crystal structure of 1·0.25H2O was determined by X-ray single crystal analysis. The rhodium(I) ion has a distorted square-pyramidal coordination. The Rh[sbnd]Cl distance (2.5908 (12) Å) is rather long, indicating weak coordination of the chloride. Dissociation of chloride in solution to produce cationic [Rh(COD)(bian)]+ ([1-Cl]+) was confirmed by ESI-MS, 1H NMR, CV and DFT calculations. Cyclic voltammetry of 1 in acetonitrile (CH3CN) showed two reversible one-electron redox waves at E1/2 = −0.36 V and −1.18 V (versus Ag/AgCl) attributable to successive reduction of the dpp-bian ligand in [1-Cl]+. DFT calculations were performed to explain the anomalously long Rh[sbnd]Cl distance and interpret the reduction sequence of 1.

AB - Reaction of [{Rh(COD)}2(μ-Cl)2] with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) has afforded a new organometallic complex [Rh(COD)(dpp-bian)Cl] (1). The crystal structure of 1·0.25H2O was determined by X-ray single crystal analysis. The rhodium(I) ion has a distorted square-pyramidal coordination. The Rh[sbnd]Cl distance (2.5908 (12) Å) is rather long, indicating weak coordination of the chloride. Dissociation of chloride in solution to produce cationic [Rh(COD)(bian)]+ ([1-Cl]+) was confirmed by ESI-MS, 1H NMR, CV and DFT calculations. Cyclic voltammetry of 1 in acetonitrile (CH3CN) showed two reversible one-electron redox waves at E1/2 = −0.36 V and −1.18 V (versus Ag/AgCl) attributable to successive reduction of the dpp-bian ligand in [1-Cl]+. DFT calculations were performed to explain the anomalously long Rh[sbnd]Cl distance and interpret the reduction sequence of 1.

KW - Acenaphthene-1,2-diimines

KW - Cyclic voltammetry

KW - DFT calculations

KW - Rhodium

KW - Synthesis

KW - Acenaphthene-1, 2-diimines

KW - HYDROGENATION

KW - DIIMINE NI(II) CATALYST

KW - REACTIVITY

KW - CRYSTAL-STRUCTURES

KW - POLYMERIZATION

KW - REDUCTION

KW - SPECTROSCOPY

KW - X-RAY

KW - VALENCE TAUTOMERISM

KW - METAL

UR - http://www.scopus.com/inward/record.url?scp=85071503660&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2019.114110

DO - 10.1016/j.poly.2019.114110

M3 - Article

AN - SCOPUS:85071503660

VL - 173

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

M1 - 114110

ER -

ID: 21467762