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• W2095216561 abstract "Abstract The rhodium(III) cationic methyl complexes, cis -[Rh(Acac)(PPh 3 ) 2 (CH 3 )(DMF)][BPh 4 ] ( 1 ) and cis -[Rh(BA)(PPh 3 ) 2 (CH 3 )(DMF)][BPh 4 ] ( 2 ) are formed upon reactions of cis -[Rh(β-diket)(PPh 3 ) 2 (CH 3 )(MeCN)][BPh 4 ] (β-diket = acetylacetonate, Acac, or benzoylacetonate, BA) with excess of dimethylformamide (DMF) in CH 2 Cl 2 solution at ambient temperature. Complexes 1 and 2 were characterized by elemental analysis, 31 P{ 1 H} and 1 H NMR spectra, and single crystal X-ray crystallography. The cations of 1 and 2 have slightly distorted octahedral geometry. The “equatorial” plane contains the β-diketonate and two PPh 3 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 β-diketonate ligand. The signals from formyl protons in the 1 H NMR spectra of 1 and 2 are shifted significantly upfield relatively to free DMF. The hydrogen bonding between formyl proton and one of the β-diketonate oxygen atoms is considered. In solutions, 1 and 2 show dynamic behavior at ambient temperature and keep their solid-state geometry at −70 °C." @default.
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• W2095216561 date "2014-12-01" @default.
• W2095216561 modified "2023-09-24" @default.
• W2095216561 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" @default.
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• W2095216561 doi "https://doi.org/10.1016/j.jorganchem.2014.09.035" @default.
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