Ytterbocenes as one- and two-electron reductants in their reactions with diazadienes: YbIII mixed-ligand bent-sandwich complexes containing a dianion of diazabutadiene |
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Authors: | Trifonov Alexander A Borovkov Ivan A Fedorova Elena A Fukin Georgii K Larionova Joulia Druzhkov Nikolai O Cherkasov Vladimir K |
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Institution: | Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, 603950, Nizhny Novgorod, GSP-445, Russia. trif@imoc.sinn.ru |
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Abstract: | Ytterbocene Yb(C(5)MeH(4))(2)(thf)(2)] reacts with diazabutadiene 2,6-iPr(2)C(6)H(3)-N=CH-CH=N-C(6)H(3)iPr(2)-2,6 (DAD) as a one-electron reductant to afford a bis(cyclopentadienyl) Yb(III) derivative containing a DAD radical anion Yb(C(5)MeH(4))(2)(dad(-.))]. However, ytterbocenes YbCp*(2)(thf)(2)] (Cp*=C(5)Me(5), C(5)Me(4)H) coordinated by sterically demanding cyclopentadienyl ligands act as two-electron reductants in their reactions with DAD. These reactions occur by abstraction of one Cp* ring and result in the formation of novel Yb(III) mixed-ligand bent-sandwich complexes, YbCp*(dad)(thf)], in which the dianion of DAD has an uncommon terminal eta(4)-coordination to the ytterbium atom. The variable-temperature magnetic measurements of complex Yb(C(5)Me(5))(dad)(thf)] suggest the existence of redox tautomerism for this compound. |
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Keywords: | diazadienes lanthanides N ligands sandwich complexes ytterbium |
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