64052-78-4

Upstream product

• 494804-05-6 dodecacarbonyltetrarhodium⁽⁰⁾ 
• 2622-14-2 tricyclohexylphosphine 
• 116466-27-4 trans-Rh(PCy₃)2(CO)(triflate) 
• 71-50-1 acetate 
• 112837-63-5 trans-Rh(PCy₃)2(CO)(ClO₄) 

Relevant academic research and scientific papers

Relative affinities of carbonylbis(triphenylphosphine)rhodium(I) and related cations for anionic ligands in CH2Cl2

Infrared spectroscopy has been used to determine the relative anion affinities in CH2Cl2 of Rh(PPh3)2(CO)+ and Rh(AsPh3)2(CO)+ via measurement of equilibrium constants for the metatheses RhL2(CO)Y + PPN+Z- = RhL2(CO)Z + PPN+Y-. Observed for L = PPh3 was the anion affinity trend NCO- ? O2CMe- ～ O2CPh- ? F- ～ NCS- > Cl- > Br- > I- ? ONO2- ～ O2CCF3- ? OTf- ～ OClO3-. A smaller series for L = AsPh3 displayed a similar trend, but with positions of NCS- and Cl- reversed. For most anion pairs studied, the equilibrium lies so far to the left or right that only limits could be calculated, given the inherent experimental limitations. For L = PPh3, the equilibrium constant for replacement of the least preferred anion by the most can be inferred as >1019. Rh(PCy3)2(CO)Cl and Rh(PCy3)2(CO)Z (Z = NCS, NCSe, O2CMe; but not F, O2CPh, and NCO) interact strongly in solution and thus limit study of that series.

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.