The syntheses of two trans-dimethylcobalt(III) complexes are reported. The complex {(CH(,3))(,2)Co(Me(,4){14}tetraeneN(,4))}ClO(,4), where (Me(,4){14}tetraeneN(,4)) is the tetradentate macrocycle 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclo-tetradeca-1,3,8,10-tetraene that coordinates cobalt in a planar fashion with two conjugated (alpha)-diimines, was prepared by standard methods via the corresponding cobalt(I) derivative. The complex (CH(,3))(,2)Co({14}tetraenato(1-)N(,4)), where ({14}tetraenato(1-)N(,4)) is the tetradentate pseudo macrocycle 2,3,9,10-tetramethyl-1,4,8,11-tetraazaundeca-1,3,8,10-tetraen-11-ol-1-olato that coordinates cobalt in a planar fashion with two conjugated (alpha)-imine-oximes, was also prepared by standard methods via the corresponding cobalt(I) derivative. The complexes were characterized by electronic, IR, and NMR spectroscopy.
The methyl-transfer reactions of the two dimethyl complexes with the metallic electrophiles, Zn('2+), Cd('2+), Pb('2+), Cr('3+), and Cu('2+) in acetonitrile were studied. The organometallic products of these reactions are dependent upon the mole ratio of M('2+)/dimethyl complex used. Reactions with the metal ion in excess produced monomethylcobalt(III) complex and an unstable CH(,3)M('n+).
When Zn('2+), Cd('2+), and Pb('2+) were reacted with excess (CH(,3))(,2)Co(chel), the products were found to be dependent upon the metal ion used. The reaction of Zn('2+) and Cd('2+) with excess dimethyl complex yielded the dimethylmetal compounds, (CH(,3))(,2)Zn and (CH(,3))(,2)Cd.
When Pb('2+) was reacted with (CH(,3))(,2)Co({14}tetraenato-(1-)N(,4)), the intermediate (CH(,3))(,2)Pb disproportionated to yield (CH(,3))(,4)Pb and Pb('0) as the ultimate products. The reaction of Pb('2+) with {(CH(,3))(,2)Co(Me(,4){14}tetraeneN(,4))}('+) is unique. Approximately 75% of the Pb('2+) added to this reaction was obtained as lead metal and 10% as (CH(,3))(,4)Pb. The data obtained suggest that a complex mechanism not observed in the other demethylation reactions is in effect.
","abstract_html":"<p>The syntheses of two trans-dimethylcobalt(III) complexes are reported. The complex {(CH(,3))(,2)Co(Me(,4){14}tetraeneN(,4))}ClO(,4), where (Me(,4){14}tetraeneN(,4)) is the tetradentate macrocycle 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclo-tetradeca-1,3,8,10-tetraene that coordinates cobalt in a planar fashion with two conjugated (alpha)-diimines, was prepared by standard methods via the corresponding cobalt(I) derivative. The complex (CH(,3))(,2)Co({14}tetraenato(1-)N(,4)), where ({14}tetraenato(1-)N(,4)) is the tetradentate pseudo macrocycle 2,3,9,10-tetramethyl-1,4,8,11-tetraazaundeca-1,3,8,10-tetraen-11-ol-1-olato that coordinates cobalt in a planar fashion with two conjugated (alpha)-imine-oximes, was also prepared by standard methods via the corresponding cobalt(I) derivative. The complexes were characterized by electronic, IR, and NMR spectroscopy.</p><p>The methyl-transfer reactions of the two dimethyl complexes with the metallic electrophiles, Zn('2+), Cd('2+), Pb('2+), Cr('3+), and Cu('2+) in acetonitrile were studied. The organometallic products of these reactions are dependent upon the mole ratio of M('2+)/dimethyl complex used. Reactions with the metal ion in excess produced monomethylcobalt(III) complex and an unstable CH(,3)M('n+).</p><p>When Zn('2+), Cd('2+), and Pb('2+) were reacted with excess (CH(,3))(,2)Co(chel), the products were found to be dependent upon the metal ion used. The reaction of Zn('2+) and Cd('2+) with excess dimethyl complex yielded the dimethylmetal compounds, (CH(,3))(,2)Zn and (CH(,3))(,2)Cd.</p><p>When Pb('2+) was reacted with (CH(,3))(,2)Co({14}tetraenato-(1-)N(,4)), the intermediate (CH(,3))(,2)Pb disproportionated to yield (CH(,3))(,4)Pb and Pb('0) as the ultimate products. The reaction of Pb('2+) with {(CH(,3))(,2)Co(Me(,4){14}tetraeneN(,4))}('+) is unique. Approximately 75% of the Pb('2+) added to this reaction was obtained as lead metal and 10% as (CH(,3))(,4)Pb. The data obtained suggest that a complex mechanism not observed in the other demethylation reactions is in effect.</p>","abstract_has_math":false,"creators":["DIMMIT, JEFFREY HOWARD"],"institution":null,"degree_name":"Doctor of Philosophy","degree_level":"Dissertation","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1980,"date_issued":"1980-01-01T08:00:00Z","date_published":"1980-01-01T08:00:00Z","updated_at":"2026-07-24T05:23:09Z","subjects":["Chemistry","Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholars.unh.edu/dissertation/1279","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["DIMMIT, JEFFREY HOWARD"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","Inorganic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://scholars.unh.edu/dissertation/1279"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The syntheses of two trans-dimethylcobalt(III) complexes are reported. The complex {(CH(,3))(,2)Co(Me(,4){14}tetraeneN(,4))}ClO(,4), where (Me(,4){14}tetraeneN(,4)) is the tetradentate macrocycle 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclo-tetradeca-1,3,8,10-tetraene that coordinates cobalt in a planar fashion with two conjugated (alpha)-diimines, was prepared by standard methods via the corresponding cobalt(I) derivative. The complex (CH(,3))(,2)Co({14}tetraenato(1-)N(,4)), where ({14}tetraenato(1-)N(,4)) is the tetradentate pseudo macrocycle 2,3,9,10-tetramethyl-1,4,8,11-tetraazaundeca-1,3,8,10-tetraen-11-ol-1-olato that coordinates cobalt in a planar fashion with two conjugated (alpha)-imine-oximes, was also prepared by standard methods via the corresponding cobalt(I) derivative. The complexes were characterized by electronic, IR, and NMR spectroscopy.
The methyl-transfer reactions of the two dimethyl complexes with the metallic electrophiles, Zn('2+), Cd('2+), Pb('2+), Cr('3+), and Cu('2+) in acetonitrile were studied. The organometallic products of these reactions are dependent upon the mole ratio of M('2+)/dimethyl complex used. Reactions with the metal ion in excess produced monomethylcobalt(III) complex and an unstable CH(,3)M('n+).
When Zn('2+), Cd('2+), and Pb('2+) were reacted with excess (CH(,3))(,2)Co(chel), the products were found to be dependent upon the metal ion used. The reaction of Zn('2+) and Cd('2+) with excess dimethyl complex yielded the dimethylmetal compounds, (CH(,3))(,2)Zn and (CH(,3))(,2)Cd.
When Pb('2+) was reacted with (CH(,3))(,2)Co({14}tetraenato-(1-)N(,4)), the intermediate (CH(,3))(,2)Pb disproportionated to yield (CH(,3))(,4)Pb and Pb('0) as the ultimate products. The reaction of Pb('2+) with {(CH(,3))(,2)Co(Me(,4){14}tetraeneN(,4))}('+) is unique. Approximately 75% of the Pb('2+) added to this reaction was obtained as lead metal and 10% as (CH(,3))(,4)Pb. The data obtained suggest that a complex mechanism not observed in the other demethylation reactions is in effect.
"]},{"key":"dc:title","label":"Title","values":["THE SYNTHESIS OF TRANS-DIMETHYLCOBALT(III) COMPLEXES OF TETRADENTATE MACROCYCLIC LIGANDS AND THEIR REACTIONS WITH METALLIC ELECTROPHILES"]}]}],"canonical_facts":{"dc:creator":["DIMMIT, JEFFREY HOWARD"],"dc:description.abstract":["The syntheses of two trans-dimethylcobalt(III) complexes are reported. The complex {(CH(,3))(,2)Co(Me(,4){14}tetraeneN(,4))}ClO(,4), where (Me(,4){14}tetraeneN(,4)) is the tetradentate macrocycle 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclo-tetradeca-1,3,8,10-tetraene that coordinates cobalt in a planar fashion with two conjugated (alpha)-diimines, was prepared by standard methods via the corresponding cobalt(I) derivative. The complex (CH(,3))(,2)Co({14}tetraenato(1-)N(,4)), where ({14}tetraenato(1-)N(,4)) is the tetradentate pseudo macrocycle 2,3,9,10-tetramethyl-1,4,8,11-tetraazaundeca-1,3,8,10-tetraen-11-ol-1-olato that coordinates cobalt in a planar fashion with two conjugated (alpha)-imine-oximes, was also prepared by standard methods via the corresponding cobalt(I) derivative. The complexes were characterized by electronic, IR, and NMR spectroscopy.
The methyl-transfer reactions of the two dimethyl complexes with the metallic electrophiles, Zn('2+), Cd('2+), Pb('2+), Cr('3+), and Cu('2+) in acetonitrile were studied. The organometallic products of these reactions are dependent upon the mole ratio of M('2+)/dimethyl complex used. Reactions with the metal ion in excess produced monomethylcobalt(III) complex and an unstable CH(,3)M('n+).
When Zn('2+), Cd('2+), and Pb('2+) were reacted with excess (CH(,3))(,2)Co(chel), the products were found to be dependent upon the metal ion used. The reaction of Zn('2+) and Cd('2+) with excess dimethyl complex yielded the dimethylmetal compounds, (CH(,3))(,2)Zn and (CH(,3))(,2)Cd.
When Pb('2+) was reacted with (CH(,3))(,2)Co({14}tetraenato-(1-)N(,4)), the intermediate (CH(,3))(,2)Pb disproportionated to yield (CH(,3))(,4)Pb and Pb('0) as the ultimate products. The reaction of Pb('2+) with {(CH(,3))(,2)Co(Me(,4){14}tetraeneN(,4))}('+) is unique. Approximately 75% of the Pb('2+) added to this reaction was obtained as lead metal and 10% as (CH(,3))(,4)Pb. The data obtained suggest that a complex mechanism not observed in the other demethylation reactions is in effect.
"],"dc:identifier":["https://scholars.unh.edu/dissertation/1279"],"dc:subject":["Chemistry","Inorganic"],"dc:title":["THE SYNTHESIS OF TRANS-DIMETHYLCOBALT(III) COMPLEXES OF TETRADENTATE MACROCYCLIC LIGANDS AND THEIR REACTIONS WITH METALLIC ELECTROPHILES"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy"]},"updated_at":"2026-07-24T05:23:09Z"}