CYCLOMETALLATION REACTIONS IN COMPLEXES OF THE TYPE Rh(oq)(CO)(P(o-BrC6F4)Ph2)

Article abstract of DOI:10.1016/0022-328X(86)80042-0

The complex (uRh(oq)Br(P(o-Cu6F4)Ph2)(H2O))2 is obtained by refluxing a solution of Rh(oq)((CO)(P(o-BrC6F4)Ph2) (oq=8-oxyquinolinat) in toluene.The structure of this compound has been determined by X-ray diffraction and refined to R=0.061 and Rw=0.065 factors.The cell has monoclinic symmetry, space group P2₁/n; a 19.513(2), b 17.049(1), c 16.898(1) angstroem and β 99.69(1) deg.The structure consits of two independent Rh(oq)Br(P(o-C6F4)Ph2)H2O) units linked by hydrogen bonds between the coordinated water molecules and oq ligands to form a distored boat (six atom ring of junction between the two units).In each unit the metal atom has a distored boat (six atom ring of junction between the two units).In each unit the metal atom has a distored octahedral coordination, with a four-atom metallocyclic ring (-uRh-P-C-Cu-) with C-Rh-P and Rh-P-C angles 69.3(2) and 85.3(3) deg, respectively, in one unit, and 70.0(2) and 81.1(2) deg in the other.The water molecule is readily displaced by a variety of phosphorus donor ligands to form the complexes uRh(oq)Br(P(o-Cu6F4)Ph2)P', P'=PPh3, P(p-CH3C6H4)3 and P(OCH3)3, in which the atoms are in trans-dispositions.