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.