Show simple item record  

dc.contributor.authorMace, Wadeen_US
dc.contributor.authorMain, Lyndsayen_US
dc.contributor.authorNicholson, Brian K.en_US
dc.date.accessioned2008-03-19T05:07:59Z
dc.date.available2007-10-22en_US
dc.date.available2008-03-19T05:07:59Z
dc.date.issued2005-07-01en_US
dc.identifier.citationMace, W.J., Main, L. & Nicholson, B.K. (2005). Reversible pyranyl complex formation and the mechanism of rearrangement to (η5-6-oxocycloheptadienyl)Mn(CO)3 complexes in the reaction of β-cyclomanganated 1,5-diarylpenta-1,4-dien-3-ones and alkynes; the crystal structure of [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese. Journal of Organometallic Chemistry, 690, 3340-3347.en_US
dc.identifier.urihttps://hdl.handle.net/10289/224
dc.description.abstract1-Phenyl-2-[(E)-3-phenylprop-2-en-1-oyl-κO]ethenyl-κC1]tetracarbonylmanganese (1a) reacts with PhCCH in CCl4 at room temperature to form [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese (2a), whose X-ray crystal structure is reported to complement that of its isomer [6-oxo-2,4,7-triphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese (3a), previously obtained from the reaction under reflux; but for 1a and PhCCPh the pyranyl complex cannot be isolated before rearrangement to the 3a analogue occurs. More forcing reaction conditions for 1a with Me3SiCCH and for [1-(2-trifluoromethylphenyl)-2-[(E)-3-(2-trifluoromethylphenyl)prop-2-en-1-oyl-κO]ethenyl-κC1]tetracarbonylmanganese (1b) with Me3SiCCH and PhCCH give new analogues of 3a where previously only 2a analogues had been isolated. The reaction in CCl4 under reflux of PhCCH and the β-deuterio analogue of 1a, [1-phenyl-2-[(E)-3-phenylprop-2-en-1-oyl-3d-κO]ethenyl-κC1]tetracarbonylmanganese, gave deuteriated 3a with exo-D at the α-carbon, C7. This is inconsistent with the Mn-mediated Ph migration mechanism originally proposed to accommodate the endo position of Ph in 3a, and instead it implicates a cyclopropyl carbonyl-addition intermediate or a cyclopropyl acyl-substitution transition state in the key rearrangement step for 2a → 3a.en_US
dc.language.isoen
dc.publisherElsevier S.A.en_NZ
dc.rightsThis article is published in the Journal of Organometallic Chemistry, (c) 2005 Elsevier B.V.en_US
dc.subjectManganeseen_US
dc.subjectAlkyneen_US
dc.subjectCyclometallationen_US
dc.subjectCrystal structureen_US
dc.subjectMechanismen_US
dc.subjectAddition-eliminationen_US
dc.subjectAcyl substitutionen_US
dc.titleReversible pyranyl complex formation and the mechanism of rearrangement to (η5-6-oxocycloheptadienyl)Mn(CO)3 complexes in the reaction of β-cyclomanganated 1,5-diarylpenta-1,4-dien-3-ones and alkynes; the crystal structure of [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganeseen_US
dc.typeJournal Articleen_US
dc.identifier.doi10.1016/j.jorganchem.2005.04.015en_US
dc.relation.isPartOfJournal of Organometallic Chemistryen_NZ
pubs.begin-page3340en_NZ
pubs.elements-id31191
pubs.end-page3347en_NZ
pubs.volume690en_NZ


Files in this item

FilesSizeFormatView

There are no files associated with this item.

This item appears in the following Collection(s)

Show simple item record