881998-41-0

Upstream product

• 591-50-4 iodobenzene 
• 691894-30-1 (N(C₆H₃(CH₃)P(CH(CH₃)2)2)2)Rh(Me)(Cl) 
• 881998-40-9 (N(C₆H₃(CH₃)P(CH(CH₃)2)2)2)Rh(Ph)(Br) 
• 591-51-5 phenyllithium 
• 676-58-4 methylmagnesium chloride 
• 1000020-66-5 [Rh(bis(o-diisopropylphosphino-p-methylphenyl)amide)(diisopropylsulfide)] 
• 108-86-1 bromobenzene 

Relevant academic research and scientific papers

Thioether, dinitrogen, and olefin complexes of (PNP)Rh: Kinetics and thermodynamics of exchange and oxidative addition reactions

A variety of (PNP)Rh-L complexes (where L = organic sulfide or sulfoxide, dinitrogen, or tertbutylethylene) have been synthesized by trapping transient (PNP)Rh (1) in situ. Equilibrium studies established the relative affinity of the (PNP)Rh fragment (1) for various L in the following ofder (of decreasing affinity): Ph2SO > SBu2n > SPhMe > dibenzothiophene > SPh2 > benzothiophene > SPr 21 > thiophene ≈ SButMe > SBu 2s ≈ H2C=CHCMe3 ? SBu 2t. Dinitrogen reacted with 1 to yield a mixture of terminal and bridging N2 complexes and was found to bind more strongly than SPr2i. Reaction of (PNP)Rh(SPr 2i) (10) with PhHal led to the corresponding oxidative addition products (PNP)Rh(Ph)(Hal) (Hal = Cl, 18a; Hal = Br, 18b; Hal = I, 18c). The relative rates of oxidative addition of PhHal to 10 were found to be in the order PhI > PhBr > PhCl. Kinetic studies of the reaction of 10 with PhBr were consistent with the reaction proceeding via reversible dissociation of SPr2i, followed by irreversible addition of PhBr. Evidence for a similar dissociative mechanism for the conversion of 10 to (PNP)Rh(S(O)Ph2) in a ligand exchange reaction was also discovered. Solid-state structures of [(PNP)Rh]2(N2) (19a) and (PNP)Rh(H2C=CHCMe3) (21) were determined using X-ray crystallography. Approximately squareplanar geometry about Rh was registered.

Carbon-halide oxidative addition and carbon-carbon reductive elimination at a (PNP)Rh center

An unsaturated (PNP)Rh fragment can be generated by means of C-C reductive elimination from (PNP)Rh(Me)(Ar) or (PNP)Rh(Ar)(Ar). This fragment undergoes carbon-halogen oxidative addition with aryl chlorides, bromides, and iodides at room temperature. The C-H oxidative addition products in reactions with haloarenes are not observed, and evidence is presented that carbon-halogen oxidative addition is thermodynamically preferred. C-C reductive elimination from (PNP)Rh(Me)(Ar) and (PNP)Rh(Ar)(Ar) proceeds near quantitatively as a clean, first-order reaction. Copyright