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      N- vs O-Coordination in cyclomanganation of 1,5-diaryl-3-(2-pyridyl)pentane-1,5-diones and 3-(2-pyridyl)chalcones; cyclomanganation at saturated carbon and the crystal structure of [1,5-diphenyl-κC2-3-(2-pyridyl- κN)pentan-2-yl-κC2-1,5-dione-κO1κO5]tetracarbonylmanganesetricarbonylmanganese

      Tully, Warren; Main, Lyndsay; Nicholson, Brian K.
      DOI
       10.1016/j.jorganchem.2005.04.016
      Link
       www.sciencedirect.com.ezproxy.waikato.ac.nz:2048
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      Tully, W., Main, L. & Nicholson, B.K. (2005). N- vs O-coordination in cyclomanganation of 1,5-diaryl-3-(2-pyridyl)pentane-1,5-diones and 3-(2-pyridyl)chalcones; cyclomanganation at saturated carbon and the crystal structure of [1,5-diphenyl-3-(2-pyridyl)pentan-2-yl-1,5-dione]tetracarbonylmanganesetricarbonylmanganese. Journal of Organometallic Chemistry, 690, 3348-3356
      Permanent Research Commons link: https://hdl.handle.net/10289/187
      Abstract
      Reaction of 1,5-diphenyl-3-(2-pyridyl)pentane-1,5-dione (5a) with 2.5 moles of benzylpentacarbonylmanganese in petroleum spirit under reflux gives a small amount of the symmetric di-aryl-manganated product [1,5-diphenyl-κC2-3-(2-pyridyl)pentane-1,5-dione-κO1κO5]bis-(tetracarbonylmanganese) (7a), but mostly [1,5-diphenyl-κC2-3-(2-pyridyl-κN)pentan-2-yl- κC2-1,5-dione-κO1κO5]tetracarbonylmanganesetricarbonylmanganese (6a) which is manganated at only one aryl carbon [by Mn(CO)4] but also [by Mn(CO)3 with N and O coordination] at the methylene carbon adjacent to the Mn(CO)4-coordinated ketone carbonyl. The latter is a rare example of direct cyclomanganation at a saturated carbon and the only known case adjacent to a carbonyl group; the X-ray crystal structure of 6a is reported. With 3 moles of benzylpentacarbonylmanganese the yield of 6a remains unchanged but some trimanganation product [1,5-diphenyl-κC2′κC2 -3-(2-pyridyl-κN)pentan-2-yl-κC2-1,5-dione-κO1κO5]tris-(tetracarbonylmanganese) (8a) is formed, presumably from 7a. Routes to products are proposed and activating factors considered. 1,5-Di-(2-thienyl)-3-(2-pyridyl)pentane-1,5-dione (5b) and its 3-thienyl isomer (5c) similarly give 6a analogues [1,5-di-(2-thienyl-κC3)-3-(2-pyridyl-κN)pentan-2-yl-κC2-1,5-dione-κO1κO5]tetracarbonylmanganesetricarbonylmanganese (6b) and [1,5-di-(3-thienyl-κC2)-3-(2-pyridyl-κN)pentan-2-yl-κC2-1,5-dione-κO1κO5]tetracarbonylmanganesetricarbonylmanganese (6c).

      Also reported are the mono-cyclomanganation product [1-(2,6-dimethoxyphenyl)-3-(2-pyridyl-κN)prop-2-en-2-yl-κC2-1-one]tetracarbonylmanganese (16) and dicyclomanganation product [1-(2,5-dimethyl-3-thienyl-κC4)-3-(2-pyridyl-κN)prop-2-en-2-yl- κC2-1-one-κO ]bis-(tetracarbonylmanganese) (17) from reaction of the respective (E)-1-aryl-3-(2-pyridyl)prop-2-en-1-ones (3-(2-pyridyl)chalcones), the first reported examples of enone metallation at the α-carbon via N-coordination by a β-2-pyridyl group.
      Date
      2005-07-01
      Type
      Journal Article
      Publisher
      Elsevier S.A.
      Rights
      This article is published in the Journal of Organometallic Chemistry, (c) 2005 Elsevier B.V.
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      • Science and Engineering Papers [3124]
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