36564-80-4Relevant academic research and scientific papers
The F/Ph rearrangement reaction of [(Ph3P)3RhF], the fluoride congener of Wilkinson's catalyst
Macgregor, Stuart A.,Roe, D. Christopher,Marshall, William J.,Bloch, Karen M.,Bakhmutov, Vladimir I.,Grushin, Vladimir V.
, p. 15304 - 15321 (2007/10/03)
The fluoride congener of Wilkinson's catalyst, [(Ph3P) 3RhF] (1), has been synthesized and fully characterized. Unlike Wilkinson's catalyst, 1 easily activates the inert C-Cl bond of ArCl (Ar = Ph, ρ-tolyl) under mild conditions (3 h at 80 °C) to produce trans-[(Ph 3P)2Rh(Ph2PF)(Cl)] (2) and ArPh as a result of C-Cl, Rh-F, and P-C bond cleavage and C-C, Rh-Cl, and P-F bond formation. In benzene (2-3 h at 80 °C), 1 decomposes to a 1:1 mixture of trans-[(Ph 3P)2Rh(Ph2PF)(F)] (3) and the cyclometalated complex [(Ph3P)2Rh(Ph2PC6H 4)] (4). Both the chloroarene activation and the thermal decomposition reactions have been shown to occur via the facile and reversible F/Ph rearrangement reaction of 1 to cis-[(Ph3P)2Rh(Ph) (Ph2PF)] (5), which has been isolated and fully characterized. Kinetic studies of the F/Ph rearrangement, an intramolecular process not influenced by extra phosphine, have led to the determination of Ea = 22.7 ± 1.2 kcal mol-1, ΔH? 22.0 ± 1.2 kcal mol-1, and ΔS? = -10.0 ± 3.7 eu. Theoretical studies of F/Ph exchange with the [(PH3)2(PH 2Ph)RhF] model system pointed to two possible mechanisms: (i) Ph transfer to Rh followed by F transfer to P (formally oxidative addition followed by reductive elimination, pathway 1) and (ii) F transfer to produce a metallophosphorane with subsequent Ph transfer to Rh (pathway 2). Although pathway 1 cannot be ruled out completely, the metallophosphorane mechanism finds more support from both our own and previously reported observations. Possible involvement of metallophosphorane intermediates in various P-F, P-O, and P-C bond-forming reactions at a metal center is discussed.
Synthesis and reactivity of fluoro complexes: Part 2. Rhodium(I) fluoro complexes with alkene and phosphine ligands. Synthesis of the first isolated rhodium(I) bifluoride complexes. Structure of [Rh3(μ3-OH) 2(COD)3](HF2) by x-ray powder diffraction
Vicente, Jose,Gil-Rubio, Juan,Bautista, Delia,Sironi, Angelo,Masciocchi, Norberto
, p. 5665 - 5675 (2008/10/09)
The reaction between [Rh(μ-OH)(COD)]2 (COD = 1,5-cyclooctadiene) and 73% HF in THF gives [Rh3(μ3-OH) 2(COD)3](HF2) (1). Its crystal structure, determined by ab initio X-ray powder diffraction methods (from conventional laboratory data), contains complex trimetallic cations linked together in 1D chains by a μ3-OH...F-H-F...HO-μ3 sequence of strong hydrogen bonds. The complex [Rh(μ-F)(COE)2]2 (COE = cyclooctene; 2), prepared by reacting [Rh(μ-OH)(COE) 2]2 with NEt3·3HF (3:2), has been characterized. Complex 1 reacts with PR3 (1:3) to give [RhF(COD)(PR3)] [R = Ph (3), C6H4OMe-4 (4), iPr (5), Cy (6)] that can be prepared directly by reacting [Rh(μ-OH)-(COD)]2 with 73% HF and PR3 (1:2:2). The reactions of 1 with PPh3 or Et3P have been studied by NMR spectroscopy at different molar ratios. Complexes [RhF(PEt3) 3] (7), [RhF(COD)(PEt3)] (8), and [RhF(PPh 3)3] (9) have been detected. The complex [Rh(F)(NBD)( iPr3P)] (NBD = norbornadiene; 10) was prepared by the sequential treatment of [Rh(μ-OMe)(NBD)]2 with 1 equiv of NEt 3·3HF and iPr3P. The first isolated bifluoride rhodium(I) complexes [Rh(FHF)(COD)(PR3)] [R = Ph (11), iPr (12), Cy (13)], obtained by reacting fluoro complexes 3, 5, and 6 with NEt3·3HF (3:1), have been characterized. The crystal structures of 3 and 11 have been determined.
The nature of the bridging nitrido ligand. Synthesis and reactivity of heterobimetallic nitrido-bridged compounds
Jones, Carolyn M.,Doherty, Nancy M.
, p. 81 - 92 (2008/10/08)
Heterobimetallic nitrido-bridged compounds (R3SiO)3V.ident.N-M(CO)(PPh3)2 (R=Me or Et and M=Ir or Rh) and (Me3SiO)3V.ident.N-Rh(PPh3)3 have beensynthesized by condensation reactions between vanadium silylimido compo unds, V(NSiR3)(OSiR3)3, and group VIII
