Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes

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• 作者：Loren C. Brown ; Emily Ressegue ; Joseph S. Merola
• 刊名：Organometallics
• 出版年：2016
• 出版时间：December 27, 2016
• 年：2016
• 卷：35
• 期：24
• 页码：4014-4022
• 全文大小：413K
• ISSN：1520-6041

文摘

The present work describes the design and synthesis of a series of rhodium and iridium dimers [(η⁵-ring)MCl]₂(μ²-Cl)₂ (where (η⁵-ring)MCl = (η⁵-Me₄C₅R)Rh(III)Cl or (η⁵-Me₄C₅R)Ir(III)Cl) using a new and efficient 1 h procedure. Rhodium and iridium dimeric complexes were synthesized via a microwave reaction. The modified HMe₄C₅R (R = isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, phenyl, benzyl, phenethyl, cyclohexyl, and cyclopentyl) type ligands were synthesized by reaction of 2,3,4,5-tetramethylcyclopent-2-en-1-one with the respective Grignard reagent (RMgX), followed by elimination of water under acidic conditions to produce the tetramethyl(alkyl or aryl)cyclopentadienes in moderate to excellent yields (40–98%). Reaction of the HMe₄C₅R ligands with [M(COD)](μ²-Cl)₂ (M = Rh, Ir; COD = 1,5-cyclooctadiene) gave the dimeric complexes [(η⁵-Me₄C₅R)MCl]₂(μ²-Cl)₂ in yields ranging from 47% to 96%. The derivatized dimers were tested for antimicrobial activity, showing activity against Mycobacterium smegmatis and improved activity with derivatized R groups against Staphylococcus aureus and MRSA 43300. The characterization of these complexes was completed by NMR spectroscopy, single-crystal X-ray diffraction, high-resolution mass spectrometry, and elemental analysis.