0000000000953985
AUTHOR
Adela Anillo
Reactions of rhodium trifluoroacetate with triphenylphosphine and pyridine. Molecular structure of Rh2(O2CCF3)4(py)4
Abstract Rh 2 (O 2 CCF 3 ) 4 reacts with two mol of triphenylphosphine forming the adduct Rh 2 (O 2 CCF 3 ) 4 (PPh 3 ) 2 . This compound in solution, even at room temperature, undergoes slow stepwise orthometalation of the phosphine ligands forming the doubly metalated compound Rh 2 (O 2 CCF 3 ) 2 [(C 6 H 4 )P(C 6 H 5 ) 2 ] 2 . This reaction has been monitored by 31 P NMR spectroscopy detecting in solution three reaction intermediates. Rh 2 (O 2 CCF 3 ) 4 reacts with excess of pyridine to form the compound Rh 2 (O 2 CCF 3 ) 4 (py) 4 that can be structurally classified as a class III adduct. It contains two bridging and two monodentate equatorial carboxylates and two equatorial and two axial…
Selective ortho-metallation reaction of the phosphine P(o-ClC6H4)Ph2. Synthesis and crystal structure of [Rh2(μ-O2CCH3)3(μ-(ClC6H3)PPh2(OH2)2]·CHCl3
Abstract From the reaction of [Rh2(O2CCH3)4(MeOH)2] in hot acetic acid with P(o-ClC6H4)Ph2, two monometallated compounds [Rh2(O2CCH3)3(C6H4)P(o-ClC6H4)Ph(HO2CCH3)2] (1), already described, and [Rh2(O2CCH3)3{(ClC6H3)PPh2}(OH2)2] have been isolated. The new compound has been characterized by an X-ray study. It crystallizes in the triclinic space group P1. It contains three acetate groups bridging a Rh24+ unit that has a Rh-Rh bond distance of 2.426(1) A; the fourth bridging ligand is derived from one P(o-ClC6H4)Ph2 metallated in the halogenated ring. The two water molecules occupy the axial coordination sites.