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Ytterbocenes as One‐ and Two‐Electron Reductants in their Reactions with Diazadienes: Yb III Mixed‐Ligand Bent‐Sandwich Complexes Containing a Dianion of Diazabutadiene
Author(s) -
Trifonov Alexander A.,
Borovkov Ivan A.,
Fedorova Elena A.,
Fukin Georgii K.,
Larionova Joulia,
Druzhkov Nikolai O.,
Cherkasov Vladimir K.
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200601481
Subject(s) - chemistry , cyclopentadienyl complex , ligand (biochemistry) , steric effects , medicinal chemistry , ring (chemistry) , bent molecular geometry , tautomer , stereochemistry , crystallography , photochemistry , catalysis , organic chemistry , biochemistry , receptor
Ytterbocene [Yb(C 5 MeH 4 ) 2 (thf) 2 ] reacts with diazabutadiene 2,6‐ i Pr 2 C 6 H 3 NCHCHNC 6 H 3 i Pr 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 η 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.