Chromium Complexes Containing Polycyclic Condensed Aromatic Ligands: Mono- and Bidirectional Synthesis from Chromium-Carbenes, Molecular Structures, and Rearrangement Reactions
Chromium–pyrenylcarbenes accessible from halopyrene precursors undergo benzannulation upon gentle warming with 3‐hexyne to give hydroquinoid benzopyrene–Cr(CO)3 complexes. Kinetic benzannulation product 3 rearranges into thermodynamic haptotropomer 4 at 70 °C in octafluorotoluene under first‐order k...
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Published in | European journal of inorganic chemistry Vol. 2014; no. 9; pp. 1462 - 1469 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Weinheim
WILEY-VCH Verlag
01.03.2014
WILEY‐VCH Verlag Wiley Subscription Services, Inc |
Subjects | |
Online Access | Get full text |
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Summary: | Chromium–pyrenylcarbenes accessible from halopyrene precursors undergo benzannulation upon gentle warming with 3‐hexyne to give hydroquinoid benzopyrene–Cr(CO)3 complexes. Kinetic benzannulation product 3 rearranges into thermodynamic haptotropomer 4 at 70 °C in octafluorotoluene under first‐order kinetics. Further complexation of 3 by Cr(NH3)3(CO)3 affords syn and anti dinuclear chromium–benzopyrene complexes. Bidirectional extension of the benzannulation protocol results in the formation of syn and anti dibenzopyrene–dichromium complexes, which are structurally characterized by X‐ray analysis.
A benzannulation/metal migration sequence allows the thermocontrolled regioselective transformation of pyrenylcarbene–chromium into hydroquinoid benzopyrene–chromium complexes. Bidirectional extension of the protocol to a 1,8‐pyrenediylbis(carbene) complex affords syn‐ and anti‐dinuclear dibenzopyrene–Cr(CO)3 complexes. TBDMS = tert‐butyldimethylsilyl, Tf = trifluoromethylsulfonyl. |
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Bibliography: | ArticleID:EJIC201301409 istex:77ED60F299760339D00B7FA3366CF18AF8A4AACB ark:/67375/WNG-WJPC7MFG-X ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1434-1948 1099-0682 |
DOI: | 10.1002/ejic.201301409 |