Abstract:A series of novel C60 rhodium complexes [Rh(acac)(L)2(η2-C60)] (L = pyridine, 4-methylpyridine, 3,5-dimethylpyridine) were prepared by the reaction of [Rh(acac)(C2H4)2] with C60 followed by treatment with pyridine or its derivatives. The molecular structure of [Rh(acac)(3,5-Me2py)2(η2-C60)]·C6H6 was determined by the X-ray crystallographic analysis.
“…The product II , obtained in analytically pure form by chromatography, was characterized by microanalysis and spectroscopy data (UV/Vis, IR, 1 H and 31 P NMR). The UV/Vis pattern of II is rather typical for transition metal η 2 ‐C 60 complexes 3,6,20. The presence of a strong ν(CO) band at 1953 cm −1 and a strong single ν(NC) band at 2153 cm −1 in the IR spectrum of II reveals both isocyanide and carbonyl ligands to be present in the molecule, pointing to a specific substitution of the triphenylphosphane ligand.…”
“…The product II , obtained in analytically pure form by chromatography, was characterized by microanalysis and spectroscopy data (UV/Vis, IR, 1 H and 31 P NMR). The UV/Vis pattern of II is rather typical for transition metal η 2 ‐C 60 complexes 3,6,20. The presence of a strong ν(CO) band at 1953 cm −1 and a strong single ν(NC) band at 2153 cm −1 in the IR spectrum of II reveals both isocyanide and carbonyl ligands to be present in the molecule, pointing to a specific substitution of the triphenylphosphane ligand.…”
“…The polymer dissolves in 3,5-dimethylpyridine, and dilution with benzene yields the five-coordinate Rh(I) complex (η 2 -C 60 )Rh(acac)(3,5-dimethylpyridine) 2 whose structure, as determined by X-ray crystallography, is shown in Figure . 41 The structure of (η 2 -C 60 )Rh(acac)(3,5-dimethylpyridine) 2 as determined by X-ray crystallography (from data in ref ).…”
Section: Other Additionsmentioning
confidence: 99%
“…The structure of (η 2 -C 60 )Rh(acac)(3,5-dimethylpyridine) 2 as determined by X-ray crystallography (from data in ref ).…”
Section: Other Additionsmentioning
confidence: 99%
“…A benzene solution of C 60 and Rh(acac)(C 2 H 4 ) 2 produces a brown precipitate with poor solubility that is presumed to be polymeric. 147 The polymer dissolves in 3,5-dimethylpyridine, and dilution with benzene yields the five-coordinate Rh(I) complex (η 2 -C 60 )Rh(acac)(3,5-dimethylpyridine) 2 whose structure, as determined by X-ray crystallography, is shown in Figure 41.…”
Complexes, Ir(CO)Cl(PR 3 ) 2 2135 2. Addition of Ir 2 (µ-Cl) 2 (η 4 -C 8 H 12 ) 2 to C 60 2144 3. Reaction of (η 5 -C 9 H 7 )Ir(CO)(η 2 -C 8 H 12 ) with C 60 2144 4. Reaction of C 60 with the Hydrogenation Catalyst, RhH(CO)(PPh 3 ) 3 2145 5. Other Additions 2145 6. Redox Reactions 2146 7. Cocrystallizations 2147 H. Platinum, Palladium, and Nickel 2147 1. Addition of M(PR 3 ) 2 Units to Fullerenes 2147 2. Formation of Pd(0) and Pt(0) Polymers 2151 3. Redox Reactions 2152 4.
Density functional theory (DFT) calculations were carried out to study the reaction mechanism of the Suzuki–Miyaura rhodium‐catalyzed hydroarylation of fullerene (C60) by phenylboronic acid in the presence of water. As found experimentally, our results confirm that addition of the phenyl group and the hydrogen atom in C60 occurs at the [6,6] bond. The rate‐determining step corresponds to the simultaneous transfer of a hydrogen atom from a water molecule to C60 and the recovery of the active species. The use of 2‐phenyl‐1,3,2‐dioxaborinane and the 4,4,5,5‐tetramethyl‐2‐phenyl‐1,3,2,‐dioxaborolane instead of phenylboronic acid as organoborate agents does not lead to great modifications of the energy profile. The possible higher steric hindrance of 4,4,5,5‐tetramethyl‐2‐phenyl‐1,3,2,‐dioxaborolane should not inhibit its use in the hydroarylation of C60. Overall, we show how organoboron species arylate C60 in rhodium‐based catalysis assisted by water as a source of protons.
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