Slow Exchange of Bidentate Ligands between Rhodium(I) Complexes: Evidence of Both Neutral and Anionic Ligand Exchange. Issue 34 (30th October 2014)

• Record Type: Journal Article
• Authors: Chen, Si; Manoury, Eric; Poli, Rinaldo
• Is Part Of: European journal of inorganic chemistry. Issue 34(2014)
• Page Start: 5820
• Page End: 5826
• Publication Date: 2014-10-30
• Subjects: Rhodium -- Ligand exchange -- Phosphine ligands -- Acetylacetonate ligands -- Cyclooctadiene ligands; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201402810
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The phosphine double exchange process involving [RhCl(COD)(TPP)] and [Rh(acac)(CO)(TMOPP)] (TPP = PPh3, TMOPP = P(C6 H4 ‐4‐OMe)3 ) to yield [RhCl(COD)(TMOPP)] and [Rh(acac)(CO)(TPP)] is very rapid but is followed by a much slower process where the bidentate ligands are exchanged to yield [Rh(acac)(COD)] and a mixture of [RhCl(CO)(TPP)2 ], [RhCl(CO)(TMOPP)2 ], and [RhCl(CO)(TPP)(TMOPP)]. The exchange involving [RhCl(COD)(L)] and [Rh(acac)(CO)(L)] yields [Rh(acac)(COD)] and [RhCl(CO)(L)2 ], where the reaction is much faster when L = TPP than when L = TMOPP. The mixed‐metal system comprising [IrCl(COD)(TPP)] and [Rh(acac)(CO)(TPP)] yields all four complexes [M(acac)(COD)] and [MCl(CO)(TPP)2 ], where M = Rh and Ir. This illustrates that both a neutral ligand exchange and an anionic ligand exchange occur. Possible pathways for these processes are discussed. Abstract : Complexes [Rh(acac)(CO)(L 1 )] and [RhCl(COD)(L 2 )] undergo a very rapid double exchange of the monodentate phosphine ligands followed by a much slower exchange process involving the bidentate ligands.