112784-14-2

Upstream product

• 494804-05-6 dodecacarbonyltetrarhodium⁽⁰⁾ 
• 104-15-4 toluene-4-sulfonic acid 
• 6476-36-4 tris(1-methylethyl)phosphine 
• 219970-52-2 2-O2S(O)C6H4Me-p>(iPr3P)2> 
• 201230-82-2 carbon monoxide 

Relevant academic research and scientific papers

Preparation, molecular structure and reactivity of mono- and di-nuclear sulfonato rhodium(I) complexes

The reaction of [Rh(η3-C3H5)(PPri 3)2] 1 or [Rh(η3-CH2Ph)(PPri3) 2] 2 with an equimolar amount of RSO3H (R = Me, p-tolyl, CF3, F, Camph) led to the formation of the monomeric sulfonatorhodium(I) complexes [Rh{η2-O2S(O)R}(PPri3) 2] 3-7 in excellent yield. An alternative route for the preparation of 4 (R = p-tolyl) and 5 (R = CF3) is based on the reaction of PPri3 with the dinuclear compounds [{Rh(C8H14)2[μ-O2S(O)R]} 2], which were obtained either from [{Rh(C8H14)2(μ-Cl)}2] 8 or [{Rh(C8H14)2(μ-OH)}2] 9 as starting materials. Compounds 3-7 react smoothly with hydrogen by oxidative addition to give the dihydridorhodium(III) complexes [RhH2{η2-O2S(O)R}(PPri 3)2]. Moreover, on treatment of 3-6 with CO and C2H4 the chelating bond of the sulfonate ligand is partially opened and the carbonyl and ethene complexes trans-[Rh{η1-OS(O)2R}(L)(PPri 3)2] (L = CO or C2H4) are formed. The bis(stibine)-rhodium(I) derivative trans-[Rh{η1-OS(O)2CF3}(C2H 4)(SbPri3)2] was obtained from [{Rh(C2H4)2[μ-O2S(O)CF 3]}2] and SbPri3. Reaction of the compounds [Rh{η2-O2S(O)CF3}(olefin)(PPri 3)] (olefin = C8H14 or C2H4) with benzene led to the displacement of the sulfonate ligand and to the formation of the half-sandwich-type complexes [Rh{η6-C6H6)-(olefin)(PPri 3)][CF3SO3] containing a rather labile benzene-rhodium bond. The preparation of the vinylidene complex trans-[Rh{η1-OS(O)C6H 4Me-p}(=C=CHPh)(PPri3)2] is also described and the crystal and molecular structures of three compounds have been determined. The four-co-ordinate sulfonato complexes 3-6 are active catalysts in the C-C coupling reaction of ethene and diphenyldiazomethane. Besides the three isomeric 1:1 adducts of C2H4 and CPh2, quite unexpectedly also the 2:1 adduct 3,3-diphenylpent-1-ene is formed.

Synthesis and Chemistry of trans-2> (X = Anionic Ligand, L = Tertiary Phosphine)

The novel preparation of a wide variety of trans-2> complexes (X = anionic ligand, L = tertiary phosphine) from , phosphine (L), and acid (HX) is described.A plausible formation pathway is proposed.The electron density on the phosphorous atom in trans-2> decreases and the length of the Rh-P bond increases with an increase in the electronegativity of the anionic ligand, X, in a cis position to the phosphine ligand.The rhodium complexes (X = arylcarboxylate) are reduced to afford rhodate anions such as - and - in hexamethylphosphoroamide solution under CO-H2.The rate of reduction increases with a decrease in the electron-withdrawing effect of the arylcarboxylate ligand.