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

Abstract

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 ofmore » 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.« less

Authors:
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
OSTI Identifier:
5516920
Resource Type:
Miscellaneous
Resource Relation:
Other Information: Thesis (Ph.D.)
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

DiVerdi, M J. Stereoselective reactions on molybdenum anti-crotyl compounds and the synthesis of chiral ruthenium imine complexes. United States: N. p., 1992. Web.
DiVerdi, M J. Stereoselective reactions on molybdenum anti-crotyl compounds and the synthesis of chiral ruthenium imine complexes. United States.
DiVerdi, M J. Wed . "Stereoselective reactions on molybdenum anti-crotyl compounds and the synthesis of chiral ruthenium imine complexes". United States.
@article{osti_5516920,
title = {Stereoselective reactions on molybdenum anti-crotyl compounds and the synthesis of chiral ruthenium imine complexes},
author = {DiVerdi, M J},
abstractNote = {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.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1992},
month = {1}
}

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