NDLI: Cyclopentadienyl chromium diimine and pyridine - imine complexes: ligand -based radicals and metal-based redox chemistry

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Cyclopentadienyl chromium diimine and pyridine - imine complexes: ligand -based radicals and metal-based redox chemistry

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Cyclopentadienyl chromium diimine and pyridine - imine complexes: ligand -based radicals and metal-based redox chemistry

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Chiang, Linus Storr, Tim Patrick, Brian O. Zhou, Wen Smith, Kevin M.
Description	Author Affiliation: Zhou W ( Department of Chemistry, University of British Columbia Okanagan, 3333 University Way, Kelowna, BC, Canada V1V 1V7.)
Abstract	Paramagnetic CpCr(III) complexes with antiferromagnetically-coupled anionic radical diimine and pyridine - imine ligands were prepared and characterized. The diimine chloro $CpCr[(ArNCR)_{2}]Cl$ complexes (1: Ar = $2,6-iPr_{2}C_{6}H_{3}$ ( Dpp ), R = H; 2: Ar = $2,6-Me_{2}C_{6}H_{3}$ (Xyl), R = Me; 3: Ar = $2,4,6-Me_{3}C_{6}H_{2}$ (Mes), R = Me) were synthesized by treatment of previously reported $Cr(diimine)(THF)_{2}Cl_{2}$ precursors with NaCp. Reduction of 1 with Zn gives $CpCr[(DppNCH)_{2}],$ 4, resulting from reduction of Cr(III) to Cr(II) with retention of the ligand -based radical. Alkoxide complexes $CpCr[(DppNCH)_{2}](OCR_{2}R′)$ (5: R = Me, R′ = Ph; 6: R = iPr, R′ = H) were synthesized by protonolysis of $Cp_{2}Cr$ with $HOCR_{2}R′$ in the presence of the neutral diimine and catalytic base. The corresponding radical pyridine -imine complexes CpCr(PyCHNMes)Cl (9), CpCr(PyCHNMes) (8), and $CpCr(PyCHNMes)(OCMe_{2}Ph)$ (11), were prepared by analogous routes. Oxidation of 8 with iodine gives CpCr(PyCHNMes)I (10) where oxidation of Cr(II) to Cr(III) again occurs with retention of the anionic pyridine - imine radical ligand . The molecular structures of complexes 1, 2, 4–8, 10 and 11 were determined by single-crystal X-ray diffraction . Unusual low energy bands were observed in the UV-vis spectra of the reported complexes, with particularly strong transitions observed for the Cr(II) complexes 4 and 8. The electronic structure of pyridine -imine complexes 8 and 10 were investigated by theoretical calculations.
ISSN	14779226
Issue Number	26
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-07-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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