The organometallic chemistry of aqueous ruthenium(II) with functionalized olefins: Complex formation, isomerization, and metathesis chain transfer
The chemistry of aqueous Ru[sup II](H[sub 2]O)[sub 6](tos)[sub 2] (tos = p-toluene sulfonate) (1) with functionalized olefins has been investigated. Complexes of the type (H[sub 2]O)[sub 5]Ru[sup II](olefin)(tos)[sub 2] are formed from 1 and monoolefins. Dienes such as diallyl ether and 1,5-hexadiene displace two aquo ligands from 1 to form chelate complexes of the type (H[sub 2]O)[sub 4]Ru[sup II](olefin)[sub 2](tos)[sub 2]. Chelation of oxygen containing functionalities such as alcohols, ethers, and sulfonates has also been observed when the functional group is a specified distance from the olefin. Olefin isomerization of allylic ethers and alcohols is catalyzed by 1 under mild conditions in aqueous solution to yield the corresponding carbonyl compounds. An exclusive 1,3-hydrogen shift is observed in the isomerization of allyl-1,1-d[sub 2] alcohol to propion-aldehyde-1,3-d[sub 2] and allyl-1,1-d[sub 2] methyl ether to 1-propenyl-1,3-d[sub 2] methyl ether. The presence of crossover products from the isomerizations of mixtures of (a) allyl-3-[sup 13]C alcohol and allyl-1,1-d[sub 2] alcohol an (b) allyl-1,1-d[sub 2] methyl ether and allyl ethyl ether demonstrates that the isomerization of both ethers and alcohols occurs via intermolecular hydrogen shifts. A modified metal hydride addition-elimination mechanism has been proposed. The acyclic terminal olefins 3-buten-1-ol and methyl acrylate are effective chain transfer agents in the ROMP 5,6-exo-bis(methoxymethyl)-7-oxabicyclo[2.2.1]hept-2-ene by 1. Oligomer samples with M[sub n] as low as 2K have been prepared. End groups corresponding to the alkylidene moieties of the chain transfer agents have been identified in the [sup 1]H and [sup 13]C NMR of the oligomer mixtures. Connectivity has been established between these end groups and the polymer chain through two-dimensional [sup 1]H NMR. Ring-opened monomer units end capped by the chain transfer agent have been identified by mass spectrometry techniques.
- Research Organization:
- California Inst. of Tech., Pasadena, CA (United States)
- OSTI ID:
- 5603335
- Resource Relation:
- Other Information: Thesis (Ph.D.)
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis and Reactivity of Palladium(II) Alkyl Complexes that Contain Phosphine-cyclopentanesulfonate Ligands
Hydride transfer in the oxidation of alcohols by (bpy)/sub 2/(py)Ru(O))/sup 2 +/. A k/sub H//k/sub D/ kinetic isotope effect of 50
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKENES
ISOMERIZATION
ORGANOMETALLIC COMPOUNDS
CHEMICAL REACTIONS
RUTHENIUM COMPLEXES
AQUEOUS SOLUTIONS
DIENES
LIGANDS
MIXTURES
POLYMERS
COMPLEXES
DISPERSIONS
HYDROCARBONS
ORGANIC COMPOUNDS
POLYENES
SOLUTIONS
TRANSITION ELEMENT COMPLEXES
400200* - Inorganic
Organic
& Physical Chemistry