Electrophilic reactivity of the dienyl ring in carbonylnitrosyl(cycloheptadienyl)manganese cations |
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| Affiliation: | 1. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China;2. Cancer Institute (Key Laboratory of Cancer Prevention and Intervention, China National Ministry of Education), The Second Affiliated Hospital, Zhejiang University School of Medicine, Hangzhou, Zhejiang 310009, China;3. Research Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, China;1. Department of Chemistry, School of Science & Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China;2. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190, China;3. Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin 300072, China;4. University of Chinese Academy of Sciences, Beijing 100049, China;1. Institute for Molecular Engineering, University of Chicago, Chicago, IL 60615, USA;2. Institute for Molecular Engineering, Argonne National Laboratory, Lemont, IL 06349, USA;1. Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, Warsaw 01-224, Poland;2. MilliporeSigma, 400 Summit Drive, Burlington, MA 01803, USA;3. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60201, USA;4. Faculty of Mathematics, Informatics, and Mechanics, University of Warsaw, 02-097 Warsaw, Poland;5. IBS Center for Soft and Living Matter and Department of Chemistry, Ulsan National Institute of Science and Technology, 50 UNIST-gil, Eonyang-eup, Ulju-gun, Ulsan 689-798, South Korea |
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| Abstract: | A kinetic study is reported for the addition of phosphorus and nitrogen donor nucleophiles to the cycloheptadienyl ring in (C7H8R)Mn(CO)(NO)L+ complexes (3, R = H, Ph; L = CO, PBu3) to give cycloheptadiene complexes (4). A substituent at the C(6) carbon in 3 does not produce any detectable steric effect, and the relative nucleophilic reactivities closely parallel those observed with other electrophilic organometallic and organic systems. The reaction 3 → 4 is the second step in the manganese-mediated conversion of a cycloheptatriene to a difunctionalized cycloheptadiene. |
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