The organometallic chemistry of aqueous ruthenium(II) with functionalized olefins: Complex formation, isomerization, and metathesis chain transfer

Thesis/Dissertation · Wed Jan 01 04:00:00 EST 1992

OSTI ID:5603335

McGrath, D V

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
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200* -- Inorganic
Organic
& Physical Chemistry
ALKENES
AQUEOUS SOLUTIONS
CHEMICAL REACTIONS
COMPLEXES
DIENES
DISPERSIONS
HYDROCARBONS
ISOMERIZATION
LIGANDS
MIXTURES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYENES
POLYMERS
RUTHENIUM COMPLEXES
SOLUTIONS
TRANSITION ELEMENT COMPLEXES