0000000000364803
AUTHOR
Antonio Tiripicchio
Fast orthometalation reactions at a binuclear dirhodium(II) complex. Synthesis, crystal structure and reactivity of Rh2(O2CCH3)3[(C6H4)PPh2]·(HO2CCH3)2
Abstract From the reaction of Rh2(O2CCH3)4(MeOH)2, in hot acetic acid with PPh3 the monometalated intermediate Rh2(O2CCH3)3[(C6H4)PPh2](HO2CCH3)2 has been isolated and characterized by an X-ray study. This compound rapidly reacts with an excess of PPh3 in dichloromethane at room temperature to give Rh2(O2CCH3)2-[(C6H4)PPh2]2(PPh3)2 with a head-to-tail structure. The same procedure at higher temperatures gives a mixture of this compound and another doubly metalated compound with a head-to-head structure.
Synthesis of orthometallated rhodium(III) compounds. Crystal structures of [RhCl2{η2(C6H4)PPh2}(η2-dppm)] and [RhCl{η2(C6H4)PPh2}(η1-PCCl)(phen)] (SbF6)·CH2Cl2 (dppm=bis(diphenylphosphino)methane; PCCl=P(o-ClC6H4)Ph2; phen=1,10 phenanthroline)
Abstract Neutral and cationic rhodium(III) metallated compounds containing a four-membered ring are prepared by different synthetic methods: (i) from rhodium(I) compounds that contain the ligand P( o -ClC 6 H 4 )PPh 2 , by 2c-2e intramolecular oxidative addition; (ii) from metallated dirhodium(II) compounds; (iii) by ligand substitution in [RhCl 2 {η 2 -(C 6 H 4 )PPh 2 }{η 2 -P( o -ClC 6 H 4 )Ph 2 }]. The crystal structures of [RhCl 2 {η 2 -(C 6 H 4 )PPh 2 }(η 2 -dppm)] ( 2 ) and of the dichloromethane solvate of [RhCl{η 2 -(C 6 H 4 )PPh 2 }{η 1 -P( o -ClC 6 H 4 )Ph 2 }(phen)](SbF 6 ) ( 11 ) have been determined by X-ray diffraction methods. In both complexes the Rh atom is in the distorted…