Rhodium(III) cationic methyl complexes containing dimethylformamide ligand, cis-[Rh(β-diket)(PPh3)2(CH3)(DMF)][BPh4] (β-diket = acetylacetonate or benzoylacetonate), in comparison with their acetonitrile analogs

E.P. Shestakova, Y.S. Varshavsky, V.N. Khrustalev, G.L. Starova, S.N. Smirnov

Research output

Abstract

The rhodium(III) cationic methyl complexes, cis-[Rh(Acac)(PPh3)(2)(CH3)(DMF)][BPh4] (1) and cis[Rh(BA)(PPh3)(2)(CH3)(DMF)][BPh4] (2) are formed upon reactions of cis-[Rh(beta-diket)(PPh3)(2)(CH3)(MeCN)][BPh4] (beta-diket = acetylacetonate, Acac, or benzoylacetonate, BA) with excess of dimethylformamide (DMF) in CH2Cl2 solution at ambient temperature. Complexes 1 and 2 were characterized by elemental analysis, P-31{H-1} and H-1 NMR spectra, and single crystal X-ray crystallography. The cations of 1 and 2 have slightly distorted octahedral geometry. The "equatorial" plane contains the beta-diketonate and two PPh3 ligands; methyl and DMF ligands occupy the axial positions. Peculiar features of complexes 1 and 2 in solid state are: (i) unusually long Rh-O(DMF) bond and (ii) non-symmetrical orientation of the formyl C-H bond in relation to two oxygen atoms of the beta-diketonate ligand. The signals from formyl protons in the H-1 NMR spectra of 1 and 2 are shifted significantly upfield relatively to free DMF. The h
Original languageEnglish
Pages (from-to)1-5
Number of pages5
JournalJournal of Organometallic Chemistry
Volume774
DOIs
Publication statusPublished - 2014

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Dimethylformamide
Rhodium
Acetonitrile
rhodium
acetonitrile
Ligands
analogs
ligands
nuclear magnetic resonance
ambient temperature
crystallography
oxygen atoms
Nuclear magnetic resonance
solid state
cations
protons
X ray crystallography
X Ray Crystallography
single crystals
geometry

Cite this

@article{fc9e7831822942d084c0130348deab42,
title = "Rhodium(III) cationic methyl complexes containing dimethylformamide ligand, cis-[Rh(β-diket)(PPh3)2(CH3)(DMF)][BPh4] (β-diket = acetylacetonate or benzoylacetonate), in comparison with their acetonitrile analogs",
abstract = "The rhodium(III) cationic methyl complexes, cis-[Rh(Acac)(PPh3)(2)(CH3)(DMF)][BPh4] (1) and cis[Rh(BA)(PPh3)(2)(CH3)(DMF)][BPh4] (2) are formed upon reactions of cis-[Rh(beta-diket)(PPh3)(2)(CH3)(MeCN)][BPh4] (beta-diket = acetylacetonate, Acac, or benzoylacetonate, BA) with excess of dimethylformamide (DMF) in CH2Cl2 solution at ambient temperature. Complexes 1 and 2 were characterized by elemental analysis, P-31{H-1} and H-1 NMR spectra, and single crystal X-ray crystallography. The cations of 1 and 2 have slightly distorted octahedral geometry. The {"}equatorial{"} plane contains the beta-diketonate and two PPh3 ligands; methyl and DMF ligands occupy the axial positions. Peculiar features of complexes 1 and 2 in solid state are: (i) unusually long Rh-O(DMF) bond and (ii) non-symmetrical orientation of the formyl C-H bond in relation to two oxygen atoms of the beta-diketonate ligand. The signals from formyl protons in the H-1 NMR spectra of 1 and 2 are shifted significantly upfield relatively to free DMF. The h",
author = "E.P. Shestakova and Y.S. Varshavsky and V.N. Khrustalev and G.L. Starova and S.N. Smirnov",
year = "2014",
doi = "10.1016/j.jorganchem.2014.09.035",
language = "English",
volume = "774",
pages = "1--5",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",

}

TY - JOUR

T1 - Rhodium(III) cationic methyl complexes containing dimethylformamide ligand, cis-[Rh(β-diket)(PPh3)2(CH3)(DMF)][BPh4] (β-diket = acetylacetonate or benzoylacetonate), in comparison with their acetonitrile analogs

AU - Shestakova, E.P.

AU - Varshavsky, Y.S.

AU - Khrustalev, V.N.

AU - Starova, G.L.

AU - Smirnov, S.N.

PY - 2014

Y1 - 2014

N2 - The rhodium(III) cationic methyl complexes, cis-[Rh(Acac)(PPh3)(2)(CH3)(DMF)][BPh4] (1) and cis[Rh(BA)(PPh3)(2)(CH3)(DMF)][BPh4] (2) are formed upon reactions of cis-[Rh(beta-diket)(PPh3)(2)(CH3)(MeCN)][BPh4] (beta-diket = acetylacetonate, Acac, or benzoylacetonate, BA) with excess of dimethylformamide (DMF) in CH2Cl2 solution at ambient temperature. Complexes 1 and 2 were characterized by elemental analysis, P-31{H-1} and H-1 NMR spectra, and single crystal X-ray crystallography. The cations of 1 and 2 have slightly distorted octahedral geometry. The "equatorial" plane contains the beta-diketonate and two PPh3 ligands; methyl and DMF ligands occupy the axial positions. Peculiar features of complexes 1 and 2 in solid state are: (i) unusually long Rh-O(DMF) bond and (ii) non-symmetrical orientation of the formyl C-H bond in relation to two oxygen atoms of the beta-diketonate ligand. The signals from formyl protons in the H-1 NMR spectra of 1 and 2 are shifted significantly upfield relatively to free DMF. The h

AB - The rhodium(III) cationic methyl complexes, cis-[Rh(Acac)(PPh3)(2)(CH3)(DMF)][BPh4] (1) and cis[Rh(BA)(PPh3)(2)(CH3)(DMF)][BPh4] (2) are formed upon reactions of cis-[Rh(beta-diket)(PPh3)(2)(CH3)(MeCN)][BPh4] (beta-diket = acetylacetonate, Acac, or benzoylacetonate, BA) with excess of dimethylformamide (DMF) in CH2Cl2 solution at ambient temperature. Complexes 1 and 2 were characterized by elemental analysis, P-31{H-1} and H-1 NMR spectra, and single crystal X-ray crystallography. The cations of 1 and 2 have slightly distorted octahedral geometry. The "equatorial" plane contains the beta-diketonate and two PPh3 ligands; methyl and DMF ligands occupy the axial positions. Peculiar features of complexes 1 and 2 in solid state are: (i) unusually long Rh-O(DMF) bond and (ii) non-symmetrical orientation of the formyl C-H bond in relation to two oxygen atoms of the beta-diketonate ligand. The signals from formyl protons in the H-1 NMR spectra of 1 and 2 are shifted significantly upfield relatively to free DMF. The h

U2 - 10.1016/j.jorganchem.2014.09.035

DO - 10.1016/j.jorganchem.2014.09.035

M3 - Article

VL - 774

SP - 1

EP - 5

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -