Syntheses and reactivities of some cyanophosphine ligands

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Saval, Ivan Harmodio
Storhoff, Bruce N.
Issue Date
Thesis (M.S.)--Ball State University.
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The ligands o-cyanophenyl(diphenyl)phosphine and bis(dimethylamino)(o-cyanophenyl) phosphine were synthesized from o-bromobenzonitrile and diphenylchlorophosphine and bis(dimethylamino)chlorophosphine, respectively. Both ligands were identified by IR, NMR and physical constant data. The reaction of bis(dimethylamino)(o-cyanophenyl)phosphine with sulfur or CH3I yields complexes of the stoichiometry [(CH3)2N]2(o-C6H4CN)P(X) (X=S, CH3I). NMR and IR spectral data suggest that the phosphorus is the site of reaction.Reaction of 2-cyanocyclohexyl(diphenyl)phosphine, 2-cyanocyclopentyl(diphenyl)phosphine or 2-cyanoethyl(dipheriyl)phosphine with M(CO)6 (M=Mo,W) and NaBH4 in refluxing ethanol yielded complexes of the stoichiometry M(CO4)L (L=2(aminomethyl)cyclohexyl(diphenyl) phosphine, 2(aminomethyl)cyclopentyl(diphenyl)phosphine, or 3-aminopropyl (diphenyl) phosphine). The infrared spectra of the complexes display two v(NH) bands at ca. 3360 cm-1 and 3308 cm-1 which are indicative of coordinated NH2 groups which result from the reduction of the CN groups. Four v(CO) bands are observed for the complexes which indicates that the compounds are of cis-configuration.Ball State UniversityMuncie, IN 47306