89363-55-3

Upstream product

• 82808-03-5 [closo-3,3-(dimethylphenylphosphine)2-3-NO₃-3,1,2-RhC₂B₉H₁₁] 
• 89363-53-1 [closo-3,3-(PMe₂Ph)2-3-H-3,1,2-RhC₂B₉H₁₁] 

Relevant academic research and scientific papers

Synthesis and structural characterisation of two η1-bonded N-phenylthioformamidate complexes of rhodium

The complexes [3-{η1-SC(H)NPh}-3,3-(PMe2Ph) 2-3,1,2-closo-RhC2B9H11] and [2-{η1-SC(H)NPh}-2,2-(PMe2Ph) 2-2,1-closo-RhTeB10H10] have been structurally characterised using X-ray crystallography and are the first η1-bonded thioformamidate complexes to be isolated.

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...

Reactions at the metal vertex of a monometal metallacarborane cluster. Chemistry of [closo-3,3-(PPh3)2-3-HSO4-3,1,2-RhC 2B9H11] and [coso-3-PPh3-3,3-NO3-3,1,2-RhC2B 9Hn]

Reaction of [closo-3,3-(PPh3)2-3-H-3,1,2-RhC2B 9H11] (1) with sulfuric or nitric acid affords [closo-3,3-(PPh3)2-3-HSO4-3,1,2-RhC 2B9H11] (2) or [closo-3-PPh3-3,3-NO3-3,1,2-RhC 2B9H11] (3), respectively. Compound 3 can also be prepared from nitric acid and the dimeric metallacarborane [{closo-Rh(PPh3)(C2B9H11)} 2] or from NO2/N2O4 and 1. Complexes 2 and 3 have been used to prepare other new metallacarboranes, namely, [closo-3-PPh3-3,3-{C(Ph)-C(PPh 3)-C(H)-C-(Ph)}-3,1,2-RhC2B9H11] (5), [{closo-3-PPh3-3-(μ-CN)-3,1,2-RhC 2B9H11}4] (7), [closo-3-PPh3-3-L-3-NO3-3,NO3-3,1,2-RhC 2B9H11] (L = CO (8); L = PPh3 (9)), [closo-3,3-(PMe2Ph)2)2-3-NO 3-3,1,2-RhC2B9H11] (10), and [closo-3-PPh3-3-CO-3-Cl-3,1,2-RhC2B9H11] (11). Complexes 5 and 7 have been characterized by X-ray crystallography. The reactions of these new metallacarboranes described herein are representative of interconversions carried out at a discrete transition-metal vertex of a cluster species. Complex 5 crystallizes in space group P1 with 2 formula units in a cell of dimensions a = 12.763 (6) A?, b = 13.348 (5) A?, c = 14.561 (7) A?, α = 91.58 (3)°, β = 93.72 (3)°, and γ = 74.64 (3)°. Data were collected at -154 °C on a Picker FACS-1 diffractometer with the θ-20 scan method. Least-squares refinement, including anisotropic vibration parameters for Rh and P and isotropic vibration parameters for other non-hydrogen atoms, with each phenyl group described as a rigid group having a single isotropic vibration parameter, led to final conventional agreement indices (on F) of R = 0.048 and Rw = 0.051, based on 4493 unique reflections having I > 3σ(I). The molecule consists of a [C2B9H11]2- cage and a triphenylphosphine ligand bound to the metal atom of the trisubstituted metallapentacycle Rh-C(Ph)-C-(PPh3)-C(H)-C(Ph). Rh-C, Rh-B, B-B, B-C, and C-C distances are normal for a 3,1,2-RhC2B9 closo rhodacarborane fragment, and the pattern of short-long-short C-C bond lengths in the RhC4 ring is reminiscent of a pentasubstituted cis-butadiene. The complex 7-5C6H6 crystallizes in space group P2/a with 4 formula units in a cell of dimensions a = 26.046 (8) A?, b = 15.626 (3) A?, c = 30.355 (8) A?, and β = 106.71 (2)°. Data were collected at -154 °C on a Syntex P1 diffractometer with the θ-20 scan method. Least-squares refinement, including vibration parameters and rigid-group assignments as described above, led to final conventional agreement indices (on F) of R = 0.063 and Rw = 0.078, based on 9732 unique reflections having I > 3σ(I). The molecules consist of four discrete closo phosphinorhodacarborane moieties joined together through their respective metal vertices by cyano ligand bridges. Each tetramer possesses a crystallographic 2-fold axis; the two noncrystallographically equivalent tetramers are very similar. The Rh-Rh separation is approximately 5 A?. Bond distances within each icosahedral fragment are normal for such a closo Rh(III) metallacarborane.