33307-64-1Relevant academic research and scientific papers
Multiple ligand transfer reaction between [CpRu(L)(AN)2][PF6] (L = AN, CO, P(OMe)3; AN = acetonitrile) and CpFe(CO)L′X (L′ = CO, PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X = Cl, Br, I)
Katayama, Taku,Onitsuka, Kiyotaka,Takahashi, Shigetoshi
, p. 31 - 37 (2007/10/03)
Treatment of ruthenium complexes [CpRu(AN)3][PF6] (1a) (AN = acetonitrile) with iron complexes CpFe(CO)2X (2a-2c) (X = Cl, Br, I) and CpFe(CO)L′X (6a-6g) (L′ = PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X = Cl, Br, I) in refluxing CH2Cl2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)2X (3a-3c) (X = Cl, Br, I) and CpRu(CO)L′X (7a-7g) (L′ = PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X = Br, I), respectively. Similar reaction of [CpRu(L)(AN)2][PF6] (1b: L = CO, 1c: P(OMe)3) causes double ligand transfer to yield complexes 3a-3c and 7a-7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]2 was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH2Cl2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe3.
Photochemistry of [(η-C5H5)Fe(η-p-xyl)]PF6 in acetonitrile solution. Characterization and reactivity of [(η-C5H5)Fe(CH3CN)3]+
Gill, Thomas P.,Mann, Kent R.
, p. 1986 - 1991 (2008/10/08)
The photolysis of [(η-C5H5)Fe(η-p-xyl)]+ (xyl = xylene) in acetonitrile solution at -40°C produces a purple intermediate that we have characterized as [(η-C5H5)Fe(CH3CN)3]+ by 1H NMR, electronic spectroscopy, and chemical reaction studies. Room-temperature photolysis of [(η-C5H5)Fe(η-p-xyl)]+ in acetonitrile also generates this species, which rapidly yields ferrocene and Fe(II) as the final products. Mechanistic studies on this system suggest that ferrocene is generated when [(η-C5H5)Fe(CH3CN)3]+ releases C5H5-, which subsequently replaces three CH3CN molecules on an unreacted [(η-C5H5)Fe(CH3CN)3]+ ion. This tris(acetonitrile) complex is a convenient starting material for the synthesis of substituted complexes of the form [(η-C5H5)Fe(CH3CN)(L)2] +, [(η-C5H5)Fe(CH3CN)(L)2] +, [(η-C5H5)Fe(L)(L′)2]+, and [(η-C5H5)Fe(L)(L′)(L″)]+, where L, L′, and L″ = isocyanides, phosphites, or phosphines. Room-temperature photolysis of [(η-C5H5)Fe(η-p-xyl)]+ in CH3CN in the presence of excess L produces [(η-C5H5)Fe(CH3CN)(L)2] +. Photolysis at -40 °C in CH3CN, followed by the addition of 1 equiv of L and a warm-up step in the presence of excess L′, produces [(η-C5H5)Fe(CH3CN)(L)(L′)] +. The reaction of the disubstituted compounds with excess ligand produces complexes of the form [(η-C5H5)Fe(L′)(L)2]+ and [(η-C5H5)Fe(L)(L′)(L″)]+, respectively. Reactivity comparisons of [(η-C5H5)Fe-(CH3CN)n(L) 3-n]+ and [(η-C5H5)Ru(CH3CN)n(L) 3-n]+ (n ≠ 0) have also been made. In every case the Fe complex has been found to undergo substitution reactions more readily than the corresponding Ru analogue.
