Hydride ligands on tri- and tetraruthenium alkylidyne clusters

Miscellaneous · Wed Jan 01 00:00:00 EST 1992

OSTI ID:5517394

Nevinger, L R

The fluxional migration of hydride ligands on a series of clusters having the general formulas ([mu]-H)[sub n]Ru[sub 3]([mu][sub 3]-[eta][sup 2]-L)(CO)[sub 9][minus]xL[sub x][sup [prime]] has been investigated using variable temperature [sup 1]H and [sup 13]C NMR spectroscopy. The cluster frameworks of HRu[sub 3](CH[sub 2]SEt)(CO)[sub 9], H[sub 2]Ru[sub 3](MeCCOMe)(CO)[sub 9], H[sub 2]Ru[sub 3](CHCO[sub 2]Me)(CO)[sub 9], and H[sub 2]Ru[sub 3] (CHCO[sub 2]Me)(CO)[sub 8](PPh[sub 3]), including the locations of the hydride ligands, have been determined by X-ray crystallography. The structure of H[sub 2]Ru[sub 3](CO)[sub 11] is assumed to be isostructural with the osmium analog. The NMR data indicated that the hydride migration on the metal framework proceeds by a step-wise mechanism along the metal-metal edges. The activation parameters were consistent with the migration occurring by bridge-terminal hydride movement. Measurement of the deuterium kinetic isotope effect for hydride fluxionality on HRu[sub 3](CH[sub 2]SEt)(CO)[sub 9] was consistent with a bridge-terminal hydride interconversion, but did not eliminate the possibility of a triply bridging transition state. The reaction of ([mu]-H)[sub 3]Ru[sub 3]([mu][sub 3]-CPh)(CO)[sub 8](NCMe) with cyclopentadiene produces two new clusters ([mu]-H)[sub 2]Ru[sub 3]([mu][sub 3]-CPh)([mu]-CO)(CO)[sub 6]([eta][sub 5]-C[sub 5]H[sub 5]) and Ru[sub 3]([mu][sub 3]-CPh)([mu]-CO)[sub 2](CO)[sub 6]([eta][sub 5]-C[sub 5]H[sub 5]). Hydrogenation of Ru[sub 3]([mu][sub 3]-CPh)([mu]-CO)[sub 2](CO)[sub 6]([eta][sup 5]-C[sub 5]H[sub 5]) gives ([mu]-H)[sub 2]Ru[sub 3]([mu][sub 3]-CPh)([mu]-CO)(CO)[sub 6]([eta][sup 5]-C[sub 5]H[sub 5]). The reaction of ([mu]-H)Ru[sub 3]([mu]-COMe)(CO)[sub 10] with either Ru(CO)[sub 5] or Ru(CO)[sub 4](C[sub 2]H[sub 4]) produces the new cluster ([mu]-H)Ru[sub 4]([mu][sub 4]-[eta][sup 2]-COMe)(CO)[sub 12].

• Research Organization: State Univ. of New York, Buffalo, NY (United States)
• OSTI ID: 5517394
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RUTHENIUM COMPLEXES
MOLECULAR STRUCTURE
ACTIVATION ENERGY
CARBON 13
CARBONYLS
DEUTERIUM
DEUTERIUM COMPOUNDS
HYDRIDES
HYDROGENATION
ISOTOPE EFFECTS
MIGRATION
NUCLEAR MAGNETIC RESONANCE
ORGANOMETALLIC COMPOUNDS
X-RAY DIFFRACTION
CARBON ISOTOPES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
ENERGY
EVEN-ODD NUCLEI
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
RESONANCE
SCATTERING
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties