Advances in Catalysis, Vol. 30 by D.D. Eley, Herman Pines, Paul B. Weisz (Eds.) PDF

By D.D. Eley, Herman Pines, Paul B. Weisz (Eds.)

ISBN-10: 0120078309

ISBN-13: 9780120078301

Particular clinical benefit and a wealth of knowledge make the ebook super precious, like different volumes within the series.(from preface)The reminiscence of the hot seventh foreign Congress on Catalysis in Tokyo continues to be with us. It used to be the most effective equipped and so much faultless and effective overseas conferences we've skilled. the area of catalytic technological know-how owes many because of the japanese organizers and hosts of the Congress.The Congress radiated the glow of a really lively progress of catalytic technological know-how and examine round the complete global. there's an evidently mounting attractiveness of the significance to society as an entire of this extensive box of molecular technology. guy has well-known extra explicitly than prior to the significance of the talents of selective conversion of molecular subject, to either the maintenance and additional evolution of man's civilization...

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Extra resources for Advances in Catalysis, Vol. 30

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Conversely, the difference of selectivity in the experiments made with flow and pulse systems (109-111), presented as an evidence for physically adsorbed precursors, can also be explained by the existence of two mechanisms with different orders versus hydrogen, due to different dehydrogenation states of the reactive species. An alternative or simultaneous explanation is that each of these mechanisms is influenced to a different extent by the hydrocarbon-tohydrogen ratio in the feed, as explained in Section 11.

That on palladium all these reactions are either negligible (internal fission, methyl shift) or nonexistent (neopentane isomerization)2 is the first argument in favor of the metallocyclobutane mechanism. Moreover, if this mechanism is operative in the isomerization of 2-methylbutane to n-pentane (Scheme 29), adsorbed ethylidene is expected to be formed instead of adsorbed methylene, as required by a metallocyclobutane mechanism for methyl shift and neopentane formation. It is well known from carbene and metallocarbene chemistry (80, 81) that substituted metallocarbenes are rapidly isomerized via 1-2 hydrogen shift to adsorbed olefins.

Although this rearrangement could be explained by the carbenoid mechanism originally proposed by Puddephatt (Scheme 27), the very distinct properties of the two classes of bond shift reactions point toward a mechanism quite different from metallocyclobutane dismutation. Therefore Rooney’s proposal might very well be more applicable than the Puddephatt rearrangement mechanism. IV. Cyclic Mechanism In a formal way, the isomerization of acyclic hydrocarbons according to a cyclic mechanism may be represented as the succession of three consecutive steps: (a) 1,5 dehydrocyclization to an adsorbed cyclopentane intermediate; (b) interconversion between isomeric adsorbed cyclopentyl intermediates, with displacement of the point@)of attachment to the metal; (c) ring cleavage, followed by desorption of the acyclic isomeric product(s).

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Advances in Catalysis, Vol. 30 by D.D. Eley, Herman Pines, Paul B. Weisz (Eds.)


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