Synthesis of ruthenium carbonyl complexes with phosphine or substituted Cp ligands, and their activity in the catalytic deoxygenation of 1,2-propanediol.
A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp(i)(Pr(4)))Ru(CO)(2)H (Cp(i)(Pr(4)) = C(5)(i-C(3)H(7))(4)H) was prepared from the reaction of Ru(3)(CO)(12) with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp(i)(Pr(4)))Ru(CO)(2)H was determined by X-ray crystallography. The ruthenium hydride complex (C(5)Bz(5))Ru(CO)(2)H (Bz = CH(2)Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO)(2)](2), was produced from the reaction of 1,2,3-trimethylindene with Ru(3)(CO)(12), and protonation of this dimer with HOTf gives {[(1,2,3-trimethylindenyl)Ru(CO)(2)](2)-(mu-H)}(+)OTf (-). A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh)(3), PCy(3), PMe(3), P(p-C(6)H(4)F)(3)] were prepared by reaction of Cp(CO)(2)RuH with added L. Protonation of (Cp(i)(Pr(4)))Ru(CO)(2)H, Cp*Ru(CO)(2)H, or CpRu(CO)[P-(OPh)(3)]H by HOTf at -80 degrees C led to equilibria with the cationic dihydrogen complexes, but H(2) was released at higher temperatures. Protonation of CpRu[P(OPh)(3)](2)H with HOTf gave an observable dihydrogen complex, {CpRu[P-(OPh)(3)](2)(eta(2)-H(2))}(+)OTf (-) that was converted at -20 degrees C to the dihydride complex {CpRu[P(OPh)(3)](2)(H)(2)}(+)OTf (-). These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H(2) (750 psi) at 110 degrees C.
Ghosh
Prasenjit
P
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000, USA.
Fagan
Paul J
PJ
Marshall
William J
WJ
Hauptman
Elisabeth
E
Bullock
R Morris
RM
D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry*; D019946:Propylene Glycol / Q000737:chemistry*; D017975:Ruthenium Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D056831:Coordination Complexes; D008024:Ligands; D010720:Phosphines; D017975:Ruthenium Compounds; D019946:Propylene Glycol; C044646:phosphine