25780-71-6Relevant academic research and scientific papers
Bicyclic bridgehead phosphoramidite (briphos) ligands with tunable π-acceptor ability and catalytic activity in the rhodium-catalyzed conjugate additions
Lee, Ansoo,Ahn, Seihwan,Kang, Kyungjun,Seo, Min-Seob,Kim, Yeonjoon,Kim, Woo Youn,Kim, Hyunwoo
supporting information, p. 5490 - 5493 (2015/02/19)
A new type of bicyclic bridgehead phosphoramidites (briphos) is reported, where the geometrical constraints significantly enhance the π-acceptor ability compared with its monocyclic analogs. The briphos is shown to be highly efficient and tunable for Rh(I
A crystallographic and DFT study on Vaska-type trans-[Rh(CO)Cl(PR3)2] complexes containing flexible ligands: The molecularstructure of trans-[Rh(CO)Cl{P(OC6H5)3 }2]
Muller, Alfred,Meijboom, Reinout,Roodt, Andreas
, p. 5782 - 5789 (2008/10/09)
An investigation into the effect of the flexibility of substituents on the disorder of the Cl-Rh-CO moiety in Vaska-type trans-[Rh(CO)Cl(PR3)2] complexes is presented. The influence of the packing of the complexes with PR3 = P(CH2C6H5)3, P(OC6H5)3, P(O-2-MeC6H4)3 and P(O-2,6-Me2C6H3)3 was evaluated by comparing the X-ray structures with the results of DFT calculations on these complexes. Reasonable agreement between the calculated and molecular structures was found. A good agreement, however, was found between the calculated and crystallographic structures when comparing the coordination polyhedronaround the Rh atom. The main difference between the calculated and soli d state structures appeared to be in the orientation of the phenyl groups of the P-donor ligands.
A facile route to carbonylhalogenometal complexes (M = Rh, Ir, Ru, Pt) by dimethylformamide decarbonylation
Serp, Philippe,Hernandez, Marc,Richard, Brigitte,Kalck, Philippe
, p. 2327 - 2336 (2007/10/03)
Dimethyl formamide (DMF) can be a convenient source of the carbonyl ligand in the coordination chemistry of rhodium, ruthenium, iridium, and platinum. We have undertaken a thorough study concerning the course of this reaction. In a first step, DMF-containing complexes are produced, which is usually accompanied by chloride redistribution. Then, upon refluxing, carbonyl species in the same oxidation state are obtained, presumably as a result of HCl-mediated DMF decomposition. Provided that water levels are kept low, reduction can occur to provide the complexes [NH2(CH3)2][RhCl2(CO) 2], [NH2(CH3)2][RuCl3(CO) 2(DMF)], [RuCl2(CO)2(DMF)2], and [NH2(CH3)2][IrCl2(CO) 2]. In the case of platinum, reduction is not effective and [NH2(CH3)2][PtCl3(CO)] is obtained. No carbonylpalladium species can be synthesized in this way, the reaction producing copious amounts of colloidal metal. Adding phosphanes to these chlorocarbonyl-containing solutions allows easy, one-step syntheses of a variety of complexes.
Substitution of CO by picolines and amines in RhCl(CO)(PR3)2. Synthesis and crystal structure of cis-RhCl(3-pic)2
Trzeciak, A. M.,Ziolkowski, J. J.,Lis, T.
, p. 391 - 398 (2007/10/02)
The title complex, cis-RhCl(3-pic)2 (3-pic = 3-picoline), has been prepared with two other isostructural rhodium complexes, respectively with 4-picoline and CH2=CH-CH2NH2.The RhCl(3-pic)2 compond crystallizes in space group P with a = 10.531(6), b = 12.025(9), c = 15.943(8) Angstroem, α = 83.01(5), β = 79.46(4), γ = 86.33(5) deg; Z = 2.The RhCl(amine)2 complexes were obtained in the reactions of 2, 2 (cod = cycloocta-1,5-diene) or RhCl(CO)2 with amines.CO substitution by amines in RhCl(CO)(PR3)2 complexes is limited by steric properties of amine and PR3 ligands. 3-Picoline substitutes CO only in complexes with PR3 ligands with cone angle Θ 140 deg.The rate of CO substitution by 2-picoline is less than half that by 3-picoline.
