Reactivity of cationic methyl rhodium(III) complexes cis-[Rh(β-diket)(PPh3)2(CH3)(CH3CN)][BPh4] toward ligands of different character: pyridine, carbon monoxide, and triphenylphosphine

A novel reaction producing the rhodium(I) complexes with π-coordinated tetraphenylborate anion, (π-PhBPh3)−. X-ray study of [Rh(PPh3)2(π-PhBPh3)]

“…reported previously [21] when their solutions (in CH 2 Cl 2 or CHCl 3 ) were kept under an inert atmosphere for days.…”

Reductive functionalization of a rhodium(iii)–methyl bond by electronic modification of the supporting ligand

“…Nevertheless, Hartwig [44][45][46] and others [47][48][49] showed that RE of R-X from Pd II can be achieved by employing sterically bulky phosphine ligands, and the Rh-based Monsanto acetic acid process has been shown to reversibly add C(sp 3 )-I 50 while ultimately eliminating C(sp 2 )-I from a Rh III center prior to acetic acid formation. 51 While the reductive functionalization from Rh III -R bonds with strong phosphorus, 52,53 oxygen, [54][55][56] and nitrogen 54 nucleophiles has been reported, the RE of alkyl halides can be challenging. Milstein and coworkers recently reported the RE of an alkyl halide from a Rh III complex using sterically bulky PCP and PNP pincer ligands to destabilize the Rh III -CH 3 moiety.…”

Trifluoroacetylacetonate rhodium(III) methyl complexes, cis-[Rh(TFA)(PPh3)2(CH3)(L)][BPh4] and cis-[Rh(TFA)(PPh3)2(CH3)(I)] (L=CH3CN, NH3, pyridine), in comparison with their acetylacetonate analogs

“…those of (P eq P ax ) 0 type, have not been described except a rather peculiar example [8]. In our previous studies only one type of (P eq P ax ) isomers was observed [11,20], namely isomers with two triphenylphosphines and CH 3 ligands lying in mutual cis position. In the case of unsymmetrically substituted b-diketonate ligand (R 1 s R 2 ), along with this kind of isomerism based on the mutual arrangement of two phosphine ligands, one more kind of isomerism appears.…”

“…The singlets at d 1.63 and 2.00 ppm differing by intensity belong to methyl groups of TFA ligands in these two isomers. Signals at 2.03 and 1.90 ppm should be assigned to methyl ligands, CH 3 (eRh), of two isomers as these signals are split into doublets with 2 J(HRh) y 2 Hz [11,12,20].…”

“…Conductivity measurements for NaBPh 4 [20] were performed too, and these data were Table 2 Selected 1 H NMR spectral parameters of methyl rhodium(III) complexes (solvent CDCl 3 ).…”