Stereoselective reactions on molybdenum anti-crotyl compounds and the synthesis of chiral ruthenium imine complexes

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

OSTI ID:5516920

DiVerdi, M J

Various methods of preparing CpMo(CO)[sub 2]([eta][sup 3]-anti-crotyl), Cp*Mo (CO)[sub 2]([eta][sup 3]-anti-crotyl), and NMCpMo(CO)[sub 2] ([eta][sup 3]-anti-crotyl), where NMCp equals neomenthylcyclopentadienyl, were evaluated. A high yielding, convenient synthesis of CpMo(CO)[sub 2] ([eta][sup 3]-anti-crotyl) was developed. A series of CpMo(NO)([eta][sup 3]-anti-crotyl)X compounds where X = I, Br, Cl, and OTs were prepared and characterized. Their reaction with aldehydes produced syn-[beta]-methyl homoallyl alcohols with high stereoselectivity. The rate of endo-exo isomerization and [Delta]G[sub +[sup +]] was determined by [sup 1]H NMR line width analysis. The rate of anti to syn isomerization and the half-life for CpMo(NO)([eta][sup 3]-anti-crotyl)X where X = I, Br, and Cl was determined. Compounds of the formula (CO)[sub 2]([eta][sup 3]-anti-crotyl)Mo(LL)Cl where LL = diphos, dppm, dppe, ethylenebis (diphenylarsine), and dipyridyl were prepared and characterized. For (CO)[sub 2]([eta][sup 3]-anti-crotyl)Mo(diphos)Cl and (CO)[sub 2]([eta][sup 3]-anti-crotyl)Mo(bipy)Cl the rate constants and [Delta]G[sub +[sup +]] for the isomerizations were determined by [sup 1]H NMR and [sup 31]P NMR line width analysis. The neutral compounds were treated with AgPF[sub 6] and CO to form the tricarbonyl species [(CO)[sub 3]([eta][sup 3]-anti crotyl)Mo(LL)]PF[sub 6] where LL = diphos, dppm, dppe, and ethylenebis (diphenylarsine). The complexes underwent nucleophilic attack to give (Z)-olefins resulting from attack on the unsubstituted carbon of the [eta][sup 3]-anti-crotyl. Chiral ruthenium imine complexes [CpRu(CO)(PPh[sub 3])(HN = CHR)]PF[sub 6] where R = Ph, C[sub 6]H[sub 4]OMe, C[sub 6]H[sub 4]NO[sub 2], CH[sub 3], and CH(Me)(Et) were prepared by metal assisted conversion of an aldehyde to an imine. The only reaction carried out was the substitution of the coordinated imine in [CpRu(CO)(PPh[sub 3])(HN = CHPh)]PF[sub 6] with I[sup [minus]] in refluxing methanol.

• Research Organization: Yale Univ., New Haven, CT (United States)
• OSTI ID: 5516920
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
MOLYBDENUM COMPOUNDS
CHEMICAL PREPARATION
ORGANOMETALLIC COMPOUNDS
STEREOCHEMISTRY
RUTHENIUM COMPOUNDS
ALCOHOLS
ALDEHYDES
CHEMICAL REACTION YIELD
CHIRAL SYMMETRY
IMINES
ISOMERIZATION
CHEMICAL REACTIONS
HYDROXY COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
SYMMETRY
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
YIELDS
400201* - Chemical & Physicochemical Properties
360601 - Other Materials- Preparation & Manufacture