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• 53687-46-0 closo-3,3-(PPh₃)2-3-H-3,1,2-RhC₂B₉H₁₁ 
• 75-09-2 dichloromethane 
• 75-57-0 tetramethlyammonium chloride 
• 97112-45-3 {(P(C₆H₅)3)2RhC₂B₉H₁₁}^(1-)*Li⁽¹⁺⁾=Li{(P(C₆H₅)3)2RhC₂B₉H₁₁} 
• 563-47-3 3-Chloro-2-methylpropene 
• 107-05-1 3-chloroprop-1-ene 

Relevant academic research and scientific papers

3-Chloro-3,3-bis(triphenylphosphine-P)-1,2-dicarba-3-rhoda-closo- dodecaborane-dichloromethane (1/1.1)

The title compound, [3,3-(PPh3)2-3-Cl-3,1,1,2-RhC2B 9H11] or [RhCl(C2H11B9)(C18H 15P)2]. 1.1CH2Cl2, contains a triangulated icosahedral closo-RhC2B9 cage. Principal bond distances are Rh - Cl 2.423 (2), Rh - P 2.373 (2) and 2.383 (2), Rh - C 2.190 (6) and 2.191 (6), and Rh - B 2.203 (8)-2.289 (8) A. The conformation of the Rh(PPh3)2Cl group above the C2B3 face of the dicarbaborane ligand is such that the Rh - Cl bond is located above the cage C - C vector.

Synthesis, structure and reactivity of a novel monocarbon hydridorhodacarborane closo-2,2-(ph3p)2-2-h-1-(me3n)-2,1 - rhcb10h10 molecular structure of 16-electron closo-2-(ph3p)-2-cl-1-(me3n)-2,1 - rhcb10h10

A novel 12-vertex monocarbon hydridorhodacarborane closo-2,2-(Ph3P)2-2-H-1-(Me3N)-2,1-RhCB10H10 1 has been synthesized by the reaction of Rh(PPh3)3Cl (2) with nido-B10H12CNMe3 (3) under alkaline conditions. At low temperature 1 exists as a mixture of two preferred conformers in solution, both having Cs symmetry, in accord with the hindered rotation of the (Ph3P)2RhH vertex with respect to the CB4 face of the monocarbon carborane cage. Complex 1 readily reacts with chlorine-containing reagents to form mononuclear 16-electron closo-2-(Ph3P)-2-Cl-1-(Me3N)-2,1-RhCB10H10 (5), whose structure was unambiguously confirmed by an X-ray diffraction study. The results of an X-ray diffraction study of the closely related dicarbon carborane derivative closo-3,3-(Ph3P)2-3-Cl-3,1,2-RhC2B9H11 (10), prepared from closo-3,3-(Ph3P)2-3-H-3,1,2-RhC2B9H11 by analogy with 5, are also reported.

Synthesis and reactions of icosahedral rhodacarboranes bearing η3-allyl, alkyl, and acyl moieties at the metal vertex

The rhodacarboranes [closo-3,3-(PPh3)2-3-H-3,1,2-RhC2B 9H11] (H(1a)) and [closo-2,2-(PPh3)2-2-H-2,1,7-RhC2B 9H11] (H(1b)) are easily converted to the corresponding anionic 1a- and 1b- by abstraction of the hydrido ligand at Rh as a proton. The formal Rh(I) species 1a- and 1b- serve as apparent nucleophiles in reactions with allyl and methallyl chlorides or allyl acetate to afford the corresponding η3-allyl derivatives. The crystal and molecular structure of [closo-3-PPh3-3-(η3-C3H 5)-3,1,2-RhC2B9H11] (2a) has been determined by X-ray diffraction techniques. The compound crystallizes in the monoclinic space group P21/c with a = 12.678 (3) A?, b = 15.391 (4) A?, c = 15.454 (2) A?, β = 121.26 (1)°, and Z = 4. Diffraction data to 2θ(max) = 50° (Mo Kα radiation) were collected on a Syntex P1 diffractometer, and the structure was solved by conventional Patterson, Fourier, and full-matrix least-squares techniques to a final discrepancy index of R = 0.041 for 3851 independent observed reflections. All atoms, including hydrogen atoms, were located. The molecule has the closo 12-vertex icosahedral geometry, and the rhodium atom exhibits pseudo-octahedral coordination with the dicarbollide ligand occupying three facial coordination sites, the triphenylphosphine occupying a fourth site, and the η3-allyl ligand filling the remaining two sites. The molecule is monomeric, and there are no intermolecular distances shorter than van der Waals distances. Reactions of 1a- and 1b- with (CH3)3OBF4 produced solvent-stabilized methyl derivatives 4a and 4b, [closo-3-PPh3-3-CH3-3-CH3COCH 3-3,1,2-RhC2B9H11] and [closo-2-PPh3-2-CH3-2-CH3COCH 3-2,1,7-RhC2B9H11], respectively. Both 4a and 4b were converted to (PPh3)2 derivatives by (CH3)2CO displacement with PPh3. Benzyl bromide and 1a- produced [closo-3-PPh3-3-PhCH2-3-Br-3,1,2-RhC2B 9H11] (6a). The corresponding 2,1,7 derivative, 6b, was similarly prepared. Dihydrogen reacts with complexes 2a, 2b, 4a, and 4b to produce unstable hydridic species 7a and 7b formulated as [closo-(PPh3)(H)(solvent)RhC2B9H11] isomers with solvent being (CH3)2CO or CH3CN. Complexes 4a and 4b react with CO (1 atm, 25°C) to produce the corresponding isomers of [closo-(PPh3)(CO)(COCH3)RhC2B9H 11] (8a and 8b, respectively). Similar benzoyl derivatives were obtained through alternative routes.

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...

Synthesis and characterization of anionic halogen-containing rhodacarboranes. Crystal and molecular structure of the hydrogen-bonded ion pair [HPPh3][closo-3-Ph3P-3,3-Br2-3,1,2-RhC 2B9H11]

The title compound was obtained in low yield from the reaction of closo-3,3-(Ph3P)2-3-H-3,1,2-RhC2B 9H11 (1) and BBr3 and was characterized by an X-ray diffraction study. Red crystals of [HPPh3][closo-3-Ph3P-3,3-Br2-3,1,2-RhC 2B9H11]·1.5C6H6, [HPPh3][3]·1.5C6H6, were triclinic, space group P1, with a = 12.591 (5) A?, b = 13.299 (4) A?, c = 17.568 (5) A?, α = 111.77 (2)°, β = 94.41 (3)°, γ = 61.24 (3)°, and Z = 2. The structure was solved by conventional heavy-atom techniques to a final discrepancy index of R = 0.046 for 6054 independent observed reflections. The rhodacarborane anion is pseudooctahedral about the rhodium atom, and the phosphonium cation is near the rhodium-bound bromine atoms with Br?H distances of 3.06 (6) and 2.70 (6) A?. It was suggested on the basis of NMR spectral data and solubility properties that ion pairing may also be significant for [HPPh3][3] in solution. It was found that K[18-crown-6][3] could be prepared in high yield from the anionic rhodacarborane K[18-crown-6] [closo-3,3-(Ph3P)2-3,1,2-RhC2B 9H11] and bromoform. The iodo analogue of 3- could be isolated as the (n-C4H9)4N+ salt, in high yield, from the reaction of closo-3-Ph3P-3,3-NO3-3,1,2-RhC2B 9H11, (n-C4H9)4NI, and NaI in dichloromethane/water. The chloro analogue of complex 3 could be prepared as the [Et4N]+ salt from the reaction of the 16-electron complex [Et4N][closo-3-Ph3P-3,1,2-RhC2B 9H11] (generated in situ) with CH2Cl2 in 60% yield.