The preparation and study of new metal binding reagents

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Authors
Mbadike, Okey P.
Advisor
Storhoff, Bruce N.
Issue Date
1990
Keyword
Degree
Thesis (M.S.)
Department
Department of Chemistry
Other Identifiers
Abstract

New phosphine ligands which also contained crown ether groups were synthesized by condensing two main reagents. Reagent A was Ph2P(CH2)3NH2 and it was prepared by reductingPh2P(CH2)2CN with LiALH4 in diethyl ether. Ph2P(CH2)2CN is obtained by reacting Ph2PH and CH2=C(H)CN in a Michael-type reaction. Reagent B, 4-formyl-benzo-15-crown-5, was obtained from the reaction of 3,4 dihydroxybenzaldehyde with 1,11 dichloro-3,6,9 trioxoundecane.By condensing the benzaldehyde crown ether and the phosphine amine, a Schiff-base type crown ether containing both P(III) and N(III) centers was obtained. Spectroscopic studies of the ligand and its Pd(II) derivative have shown PdCl2[Ph2P.(CH2)3N CH-C6H3(OMe)2]2 were characterized by that metal binding occurred exclusively on the P( III) center.A model ligand was synthesized by condensing 3,4-dimethoxybenzaldehyde with Ph2P(CH2)3NH2 to obtain an analogous product. Both ligands, Ph2P(CH2)3N=CH-benzo-15crown-5 and Ph2P(CH2)3N=CH -C6H3(OMe)2 and their palladium derivatives, PdCl2[Ph2P(CH2)3N=CH-benzo-15-crown-5]2 and spectroscopic and elemental analysis. The Pd(II) derivatives were synthesized from the reactions of (Ph2CN)2)PdC12 with the ligands.

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