36713-96-9

Upstream product

• 34774-42-0 Rh(CO)2Cl(P(CH₃)2C₆H₅) 
• 672-66-2 Dimethyl(phenyl)phosphine 
• 51048-30-7 (cyclohexylthio)trimethylsilane 
• 22685-99-0 trans-carbonylchlorobis(dimethylphenylphosphine)iridium(I) 
• 35972-23-7 [RhCl₃(CO)(dimethylphenylphosphine)2] 

Downstream Products

• 14882-42-9 mer-RhCl3(PMe2Ph)3 
• 75215-21-3 [Rh(CO)(PMe₂Ph)2(CH₃COCH₃)][ClO₄] 
• 35972-23-7 [RhCl₃(CO)(dimethylphenylphosphine)2] 
• 15691-93-7 trans-RhCl(CO)(PEt₂Ph)2 
• 95827-55-7 K⁽¹⁺⁾*Rh(CO)3(PC₆H₅(CH₃)2)^(1-)=K{Rh(CO)3(PC₆H₅(CH₃)2)} 
• 77018-12-3 [RhCl₃(CO)(P(C₂H₅)2C₆H₅)(P(CH₃)2C₆H₅)] 

Relevant academic research and scientific papers

31P and 13C NMR investigation of the system tetracarbonyldi-μ-chlorodirhodium(I)-tertiary phosphine

13C and 31P NMR data at low temperature prompted us to characterize cis- (3) (3a, PR3 = PPh3; 3b, PR3 = PMe2Ph), as surprisingly stable products of the reaction between 2> (1) and tertiary phosphines in toluene (P : Rh = 1).Every attempt to isolate solid 3a led to the cis- and trans- halide-bridged dimers 2> (5a) and 6a which are formed from 3a by slow decarbonylation, a process which is greatly accelerated by the evaporation of the solvent under vacuum.The analogous reaction of 1 with dimethylphenylphosphinefollows a similar pathway; in this case, however, low temperature NMR spectra allowed us to characterize the pentacoordinated dinuclear species 2> (2b) as the unstable intermediate of the bridge-splitting process.The reaction of 3 with a second equivalent of phosphine (P : Rh = 2) leads, at room temperature, to the well known product trans- (8) accompanied by evolution of CO; however our data show that when the reaction is performed at 200 K, decarbonylation is prevented and spectroscopic evidence of trigonal bipyramidal pentacoordinate (7), stable only at low temperature, can be obtained.

Direct Oxidative Addition-Reductive Elimination Reactions Between trans- and or trans- (M = Rh or Ir, L = tertiary phosphine)

Complexes of the type trans- and .M = Rh or Ir, L = PMe2Ph or PEt2Ph, have been shown to react with each other, presumably by a double chloro-bridged intermediate, and undergo rapid oxidative addition-reductive elimination; phosphine exchange is much slower.Similar results were obtained when trans- was treated with trans-, M = Rh or Ir, for which rapid and complete conversion into trans- and occured. (31)P NMR data are given.