79027-52-4

Upstream product

• 1333-74-0 hydrogen 
• 67-64-1 acetone 

Downstream Products

• 116766-92-8 {Rh(H)2(3,6-bis(2'-pyridiyl)pyridazine)(triphenylphosphine)2}PF₆*CH₂Cl₂ 
• 850199-99-4 [N,o-C-(p-methoxy-phenylmethylbenzylaminato)]hydrido(acetone)bis(triphenylphosphine)rhodium(III) hexafluorophosphate 

Relevant academic research and scientific papers

RATES AND ACTIVATION PARAMETERS FOR SOLVENT EXCHANGE WITH (1+) (M = RhIII OR IrIII, R = CYCLOHEXYL OR PHENYL) CATIONS

Using 1H n.m.r. line-broadening and, where possible, stopped-flow Fourier-transform n.m.r., rates and activation parameters have been determined for solvent exchange with complexes of the type (1+) (M = RhIII or IrIII; R = phenyl, solvent = MeCN or Me2CO; R = cyclohexyl, solvent = MeCN) in 2H2>-dichloromethane solution.In all cases the co-ordinated solvent molecules are in trans positions with respect to the hydride ligands, and at 298 K the various complexes have rate constans for solvent exchange (k1) which differ almost by a factor of 107; k1(Rh) > k1(Ir) because for analogous species ΔH(Rh) (Ir), and the acetone solvates are much more labile than the acetonitrile complexes because of lower ΔH values.Values of ΔS are significantly positive (8-32 J K-1mol-1 when M = RhIII, 25-30 J K-1mol-1 when M= IrIII) in line with a dissociative, D mechanism.Hydrogen-1 n.m.r. spectra of (1+) and (1+) ions (L = MeOH, MeCN, pyridine, styrene, or cyclo-octene) are reported and compared.