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- W3212491479 endingPage "25589" @default.
- W3212491479 startingPage "25572" @default.
- W3212491479 abstract "Haliranium ions are intermediates often involved in complex cyclisations, where their structure allows for control over stereospecific outcomes. Extending previous studies into their structure and reactivity in the gas phase, this work focuses on the bimolecular reactivity of ethyl bromiranium and iodiranium ions with cyclic alkenes. The products observed via mass spectrometry were broadly attributed to either addition by cyclohexene at the iranium carbon or attack at the heteroatom to undergo associative π-ligand exchange. The model proposed was supported by both kinetic experiments and DFT calculations, where the rate of parent ion consumption proceeded at the collision rate (Br: k2 = 1.25 × 10-9 and I: k2 = 1.28 × 10-9 cm3 molecule-1 s-1) with the subsequent partitioning dependent on the relative stability of the initial intermediates and the relatively large barriers present in the addition pathway. Exploration of the effect of cycloalkene ring strain on the iodiranium ion reactivity was conducted with a series of crossover experiments with 50 : 50 mixtures of either cyclohexene or cis-cyclooctene and styrene, where the outcomes were dependent on the competing ring strain relief gained by reaction with each neutral. The nature of the exchange transition state was determined to be pseudocoarctate following both natural bond orbital (NBO) and anisotropy of the induced current density (ACID) analysis." @default.
- W3212491479 created "2021-11-22" @default.
- W3212491479 creator A5004403965 @default.
- W3212491479 creator A5005418504 @default.
- W3212491479 creator A5048563759 @default.
- W3212491479 creator A5090590988 @default.
- W3212491479 date "2021-01-01" @default.
- W3212491479 modified "2023-10-14" @default.
- W3212491479 title "Experimental and theoretical investigations into the mechanisms of haliranium ion π-ligand exchange reactions with cyclic alkenes in the gas phase" @default.
- W3212491479 cites W1930483626 @default.
- W3212491479 cites W1958433582 @default.
- W3212491479 cites W1966396675 @default.
- W3212491479 cites W1969886997 @default.
- W3212491479 cites W1970583032 @default.
- W3212491479 cites W1971488634 @default.
- W3212491479 cites W1976074105 @default.
- W3212491479 cites W1977950936 @default.
- W3212491479 cites W1981995666 @default.
- W3212491479 cites W1982218536 @default.
- W3212491479 cites W1983098306 @default.
- W3212491479 cites W1983889049 @default.
- W3212491479 cites W1986703409 @default.
- W3212491479 cites W1987137984 @default.
- W3212491479 cites W1988091937 @default.
- W3212491479 cites W1988182123 @default.
- W3212491479 cites W1990647386 @default.
- W3212491479 cites W1991630355 @default.
- W3212491479 cites W2006315812 @default.
- W3212491479 cites W2009325158 @default.
- W3212491479 cites W2015967306 @default.
- W3212491479 cites W2016474226 @default.
- W3212491479 cites W2019732897 @default.
- W3212491479 cites W2023964245 @default.
- W3212491479 cites W2024438285 @default.
- W3212491479 cites W2024447593 @default.
- W3212491479 cites W2024777137 @default.
- W3212491479 cites W2028046413 @default.
- W3212491479 cites W2029972327 @default.
- W3212491479 cites W2031384860 @default.
- W3212491479 cites W2035883315 @default.
- W3212491479 cites W2036286299 @default.
- W3212491479 cites W2039293281 @default.
- W3212491479 cites W2040722184 @default.
- W3212491479 cites W2040777200 @default.
- W3212491479 cites W2045787143 @default.
- W3212491479 cites W2047355538 @default.
- W3212491479 cites W2047652018 @default.
- W3212491479 cites W2047898578 @default.
- W3212491479 cites W2048577460 @default.
- W3212491479 cites W2049822504 @default.
- W3212491479 cites W2052014622 @default.
- W3212491479 cites W2052193694 @default.
- W3212491479 cites W2052732897 @default.
- W3212491479 cites W2067570011 @default.
- W3212491479 cites W2069308701 @default.
- W3212491479 cites W2069796488 @default.
- W3212491479 cites W2070079148 @default.
- W3212491479 cites W2072258521 @default.
- W3212491479 cites W2081907407 @default.
- W3212491479 cites W2086190383 @default.
- W3212491479 cites W2090444359 @default.
- W3212491479 cites W2090756080 @default.
- W3212491479 cites W2092157292 @default.
- W3212491479 cites W2095489436 @default.
- W3212491479 cites W2096768296 @default.
- W3212491479 cites W2097780295 @default.
- W3212491479 cites W2098886669 @default.
- W3212491479 cites W2099796414 @default.
- W3212491479 cites W2112850441 @default.
- W3212491479 cites W2119651057 @default.
- W3212491479 cites W2138384257 @default.
- W3212491479 cites W2150697053 @default.
- W3212491479 cites W2274172752 @default.
- W3212491479 cites W2316977078 @default.
- W3212491479 cites W2317374997 @default.
- W3212491479 cites W2326656346 @default.
- W3212491479 cites W2329199794 @default.
- W3212491479 cites W2334064032 @default.
- W3212491479 cites W2342714527 @default.
- W3212491479 cites W2411333122 @default.
- W3212491479 cites W2471170444 @default.
- W3212491479 cites W2509700200 @default.
- W3212491479 cites W2617387345 @default.
- W3212491479 cites W2652280586 @default.
- W3212491479 cites W2784327342 @default.
- W3212491479 cites W2794291180 @default.
- W3212491479 cites W2918890689 @default.
- W3212491479 cites W2950139951 @default.
- W3212491479 cites W2950386231 @default.
- W3212491479 cites W2950482969 @default.
- W3212491479 cites W2950995052 @default.
- W3212491479 cites W2962838283 @default.
- W3212491479 cites W2965821836 @default.
- W3212491479 cites W2973090774 @default.
- W3212491479 cites W2982825005 @default.
- W3212491479 cites W3034310241 @default.
- W3212491479 cites W3043013501 @default.
- W3212491479 cites W3083507858 @default.