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Degree

Doctor of Philosophy, Case Western Reserve University, Chemistry, 2005.

Abstract

There are many similarities between phosphaalkenes and phosphaalkynes, low-coordinate phosphorus compounds containing RP=CR₂ and RC≡P functional groups, and olefins (R2C=CR₂), their unsaturated carbon analogues. Phosphanylidene-σ⁴-phosphoranes have proven to be phospha-Wittig reagents that react with aldehydes to generate phosphaalkenes. Using the phospha-Wittig reaction, phosphaalkene oligomers and polymers were synthesized and characterized and shown to exhibit bathochromic shifts in comparison with related olefins. meta-Terphenyl phosphaalkynes have also been prepared. These materials were prepared for possible synthesis of transition metal complexes of phosphaalkynes. In addition, phosphanylidene-σ⁴-phosphoranes react with ortho-quinones to form 1,3,2-dioxaphospholanes or β-phosphaenones depending on the nature of the quinone. Furthermore, meta-terphenyls containing methoxy groups were investigated which have different properties from those having alkyl substitutents. 2,6-Dimesitylphenyl difluorophosphine was synthesized and characterized and found to be relatively inert to reduction by active magnesium.

Keywords

phosphaalkenes; phosphaalkynes; Phosphanylidene-σ⁴-phosphoranes; phospha-Wittig reaction; phosphaalkene oligomers and polymers; meta-Terphenyl phosphaalkynes; 1,3,2-dioxaphospholanes; β-phosphaenones

Advisor

John D. Protasiewicz

Pages

224p.

Document number: case1102137178
Permalink: http://rave.ohiolink.edu/etdc/view?acc_num=case1102137178

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