76146-56-0

Upstream product

• 76166-14-8 [(CH₂CHCH₂CH₂)(H)(P(C₆H₅)3)RhC₂B₉H₁₀] 
• 14694-95-2 tris(triphenylphosphine)rhodium(l) chloride 
• 14694-95-2 Wilkinson's catalyst 

Relevant academic research and scientific papers

Metallacarboranes in Catalysis. 2. Synthesis and Reactivity of Closo Icosahedral Bis(phosphine)hydridorhodacarboranes and the Crystal and Molecular Structures of Two Unusual closo-Phosphinerhodacarborane Complexes

A series of closo icosahedral rhodacarboranes bearing substituents at carbon has been synthesized by the reaction of with the correspondingly C-substituted nido-carborane anions: from (1-) where R = R' = H; R = R' = D; R = H and R' = Ph, Me, and n-Bu; from (1-) where R = H, Ph, and Me; and from (1-).These closo icosahedral rhodacarboranes are catalytically active in alkene isomerization and hydrogenation reactions, among others.The B-D-B-bridge deuterated (1-) gave when reacted with , establishing the regiospecific transfer of BHB hydrogen to Rh-H in the synthesis reaction.The complex is apparently transformed to by a polytopal rearrangement under mild conditions.The optically active catalyst was employed to hydrogenate ethyl α-phenylacrylate to give ethyl α-phenylpropionate in 3percent enantiomeric excess.In the absence of hydrogen this chiral catalyst reacted with certain esters of the acrylic type to yield alkyl chelates in which the alkene function of the ester had undergone migratory insertion into the Rh-H and the ester carbonyl oxygen became bound to Rh.One of these chelates, derived from the d-catalyst and n-butyl acrylate, was characterized crystallographically.The compound crystallizes in the space group P212121 with unit cell parameters a = 24.578 (5) Angstroem, b = 12.543 (2) Angstroem, and c = 10.377 (2) Angstroem, four molecules per unit cell.The structure was solved by conventional heavy-atom methods and refined to a final value of R = 0.069, Rw = 0.080 (3159 reflections).The absolute configuration of the d-catalyst and the (1-), from which it was derived, was thus established.Reaction of the unsubstituted compounds and (L = PPh3) with more basic phosphines gave the corresponding L2 compounds with L = PEt3, PMe2Ph, and for the 3,1,2-isomer, L2 = Ph2PCH2CH2PPh2.Reaction of the unsubstituted 3,1,2-isomer (L = PPh3) with HCl in CHCl3 gave .The analogous chloro compound in which L = PMe2Ph was prepared by the reaction of the Rh-H species with CH2Cl2.Reaction of with HCl/CHCl3 produced the coordinatively unsaturated 16-electron species .This complex reacted with CO and ligands to produce coordinatively saturated adducts.A crystallographic study of the 16-electron 2,1,7-chloride was carried out.This compound crystallizes in the monoclinic system P21/n, a = 13.840 (5) Angstroem, b = 17.000 (7) Angstroem, c = 13.771 (6) Angstoem, and β = 118.98 (2) deg, four molecules of complex and...

A designed metallacarborane catalyst. Synthesis, structure, and reactions of [closo-1,3-[μ-(η2-3-CH2=CHCH2CH 2)]-3-H-3-PPh3-3,1,2-RhC2B9H 10]

The synthesis and reactions of a designed metallacarborane catalyst, [closo-1,3-[μ-(η2-3-CH2=CHCH2CH 2)-3-H-3-PPh3-3,1,2-RhC2B9H 10] (I), are reported. Complex I contains a chelating 4-butenyl side chain attached to the dicarbollide ligand, the alkenyl function of which formally replaces one of the triphenylphosphine ligands of the parent compound [closo-3-H-3,3-(PPh3)2-3,1,2-RhC2B 9H11] (II). When I was exposed to conditions employed for the hydrogenation of alkenes or alkynes, the alkenyl ligand was hydrogenated to a noncoordinating butyl group, leaving an open coordination site on rhodium which greatly enhanced the rate of hydrogenation of added alkene. Complex I was, indeed, found to be among the most active homogeneous hydrogenation catalysts reported. Complex I also catalyzed the isomerization of hex-1-ene. The crystal and molecular structure of I has been determined by three-dimensional X-ray diffraction techniques. The compound crystallizes in the monoclinic space group P21/a with a = 16.494 (4) A?, b = 11.193 (2) A?, c = 17.006 (3) A?, β = 122.49 (1)°, and Z = 4. The observed and calculated densities are 1.229 and 1.386 g cm-3, respectively. Diffraction data to 2θ maximum = 45° (Mo Kα radiation) were collected on a Syntex P1 automated diffractometer, and the structure was solved by conventional Patterson, Fourier, and full-matrix least-squares techniques to a final discrepancy index of R = 0.044 for the 2253 independent observed reflections. All atoms, including hydrogen atoms, were located. The molecule has the closo 12-vertex icosahedral geometry, and the rhodium is bonded to one hydrogen atom and one triphenylphosphine ligand and π bonded to the alkene function as well as symmetrically bonded to the C2B3 face of the C2B9 dicarbollyl group. The molecule is monomeric, and there are no intermolecular distances shorter than van der Waals distances. The reactions of I with hydrogen in the presence and absence of triphenylphosphine are reported.

Precursor of an Extraordinarily Reactive Homogeneous Hydrogenation Catalyst. Synthesis, X-Ray Crystal Structure and Reactions of 2-3,4-CH2:CHCH2CH2)-3-H-3-PPh3-3,1,2-RhC2B9H10>

The synthesis, X-ray crystal structure, and reactions of the catalyst precursor, the title compound (1), and the initial rates of some alkene hydrogenations catalysed by (1) are reported.