ISSN:
0025-116X
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Polymeric cobalt dinitrogen complexes were synthesized by two different methods: by the ligand substitution reaction of polymers 5a - c and 6a - c, containing 4-diphenylphosphinophenylethylene units (3) or 4-diphenylphosphinomethylphenylethylene units (4), respectively, with hydridodinitrogentris(triphenylphosphine)cobalt(I) (CoH(N2)(PPh3)3), or by the direct reaction of tris(acetylacetonato)cobalt(III) with triphenylphosphine, the polymers 5a - c or 6a - c, and triisobutylaluminium under nitrogen. The intensity of the vN2 band in the IR spectrum of the polymeric dinitrogen complex was found to be about four times as that of CoH(N2)(PPh3)3. Ammonia was formed after hydrolysis of the complex, which was prepared by mixing a tetrahydrofuran solution of naphthaline, lithium, and titanium tetrachloride with the polymeric dinitrogen complex. The yields of ammonia in the case of the polymeric complexes were high in comparison with that obtained with CoH(N2)(PPh3)3. The highest yields of ammonia were obtained when a mole ratio [P̄]/[Co] 〈 1 ([P̄] is the concentration of phosphino groups in the polymer and [Co] is that of Co in CoH(N2)(PPh3)3), a temperature of -20°C, and a reaction time of 1 h were applied.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/macp.1981.021820201
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