0000000000171752
AUTHOR
Francisco Barceló
Cyclometallation reactions in complexes of the type Rh(oq)(CO)(P(o-BrC6F4)Ph2)
Abstract The complex [uRh(oq)Br(P( o -Cu 6 F 4 )Ph 2 )(H 2 O)] 2 is obtained by refluxing a solution of Rh(oq)(CO)(P( o -BrC 6 F 4 )Ph 2 ) (oq = 8-oxyquinolinate) in toluene. The structure of this compound has been determined by X-ray diffraction and refined to R = 0.061 and R w = 0.065 factors. The cell has monoclinic symmetry, space group P 2 1 / n ; a 19.513(2), b 17.049(1), c 16.898(1) A and β 99.69(1)°. The structure consists of two independent Rh(oq)Br(P( o -C 6 F 4 )Ph 2 )H 2 O) units linked by hydrogen bonds between the coordinated water molecules and oq ligands to form a distorted boat (six atom ring of junction between the two units). In each unit the metal atom has a distorted oc…
Cyclometallation reactions in complexes of the type Rh(oq)(CO)(P(o-BrC6F4)Ph2)
Abstract The reaction of Rh(oq)(CO)(PCBr) (PCBr = P(o-BrC6F4)Ph2; oq = 8-oxyquinolinte)_ in refluxing toluene in the presence of Et4NBr (1/4 molar ratio) gives Rh(oq)Br(PC) (H2O), PC = P (o-C6F4)Ph2, in practically quantitative yield. The water molecule is readily displaced by various P-donor ligands to give complexes of general formula Rh(oq)Br(PC) PR3 (PR3 = PPh3, P(p-MeC6H4)3, P(p-MeOC6H4)3, P(p-FC6H4)3, P(PMe)3 and P(OPh3). The molecular structure of the compound Rh(oq)Br(PC) (PPh3) has been determined by X-ray methods. Crystals of the title compound are monoclinic, space group P21/n with unit cell dimensions a 11.273(4), b 20.087(8), c 17.471(7) A and β 102.15(8)°. The final R for 2304…
Cyclometallation reactions in complexes of the type Rh(oq)(CO)[P(o-BrC6F4)Ph2]. The molecular structure of F4)Ph2] (oq = 8-hydroxyquinolinate)
Cyclometallation occurs when a solution of the complex Rh(oq)(CO)(PCBr), (PCBr = 2-bromo-3,4,5,6-tetrafluorophenyldiphenylphosphine; oq = 8-hydroxyquinolinate) in toluene is refluxed, giving Rh(oq)2(PC) (PC = P(C6F4)(C6H5)2) and a dimeric compound, not yet completely characterized, formulated as Rh2Br(oq)(PCBr)2. Rh(oq)2(PC) was characterized by elemental analysis, by conductance measurements, and by 19F, 31P NMR and infrared spectroscopy. Its molecular structure was determined by single-crystal X-ray methods and refined by standard procedures to final agreement factors R and Rw of 0.067 and 0.060 for 5346 observed data. Lattice constants are 15.8494(6), 14.7188(5), 14.6675(5) A and β 96.93…
Synthesis of Cyclometalated Rhodium(III) Complexes. Study of the Carbonyl Insertion Reactions into the Rh-C Bond of the Metalocycle
Abstract In this paper we report the preparation of new orthometalated rhodium(III) compounds of the formula Rh(oq)(AB)(PC), from Rh(oq)(Br)(PC)(H20), AB being a bidentade anionic ligand, oq= 8-oxyquinolate and PC = P(o-C6F4)Ph2. Their redox behaviour is also described. The reaction of Rh(Oq)(Br)(PC)(H20) [Oq = 5-Me-8-oxyquinolate (5-Meoq), 8-oxyquinolate] with carbon monoxide under pressure leads to expansion of the metalocycle ring by CO insertion into the Rh-C bond.