Room-Temperature Alkane Reactivity in Zeolites: An H/D Exchange Study

被引：15

作者：

Sido, Abdelkarim Sani Souna ^{[1
]}

Walspurger, Stephane ^{[1
]}

Barbiche, Jeremy ^{[1
]}

Sommer, Jean ^{[1
]}

机构：

[1] Inst Chim Strasbourg, CNRS, UMR 7177, Inst Chim Associe, F-67000 Strasbourg, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 10期

关键词：

alkanes; carbocations; isotopic labeling; reaction mechanisms; solid acids; HYDROGEN-DEUTERIUM EXCHANGE; BRONSTED ACID SITES; H BOND ACTIVATION; SOLID ACIDS; QUANTITATIVE-DETERMINATION; NMR OBSERVATION; AB-INITIO; ISOBUTANE; IONS; REARRANGEMENT;

D O I：

10.1002/chem.200902624

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

As evidenced by H/D exchange with acidic zeolites, isoalkanes react readily at room temperature whereas linear alkanes do not. The observed regioselectivity of the exchange process demonstrates that the main factor controlling the reaction is not the accessibility to the acid sites, but the intrinsic reactivity of the alkane. The mechanism is best rationalized by classic organic chemistry involving carbocationic intermediates including the Markovnikov rule.

引用

页码：3215 / 3221

页数：7

共 49 条

[1] HYDROGEN EXCHANGE REACTIONS OF THE BUTANES IN SULFURIC ACID [J].

BEECK, O ;

OTVOS, JW ;

STEVENSON, DP ;

WAGNER, CD .

JOURNAL OF CHEMICAL PHYSICS, 1949, 17 (04) :418-419

[2] Are carbenium and carbonium ions reaction intermediates in zeolite-catalyzed reactions? [J].

Boronat, M. ;

Corma, A. .

APPLIED CATALYSIS A-GENERAL, 2008, 336 (1-2) :2-10

[3] Reaction intermediates in acid catalysis by zeolites: Prediction of the relative tendency to form alkoxides or carbocations as a function of hydrocarbon nature and active site structure [J].

Boronat, M ;

Viruela, PM ;

Corma, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (10) :3300-3309

[4] NAMES FOR HYDROGEN-ATOMS, IONS, AND GROUPS, AND FOR REACTIONS INVOLVING THEM [J].

BUNNETT, JF ;

JONES, RAY .

PURE AND APPLIED CHEMISTRY, 1988, 60 (07) :1115-1116

[5] INORGANIC SOLID ACIDS AND THEIR USE IN ACID-CATALYZED HYDROCARBON REACTIONS [J].

CORMA, A .

CHEMICAL REVIEWS, 1995, 95 (03) :559-614

[6] Studies based on deuterium isotope effect on 13C chemical shifts [J].

Dziembowska, T ;

Hansen, PE ;

Rozwadowski, Z .

PROGRESS IN NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY, 2004, 45 (1-2) :1-29

[7] Theoretical and experimental investigation of the effect of proton transfer on the 27Al MAS NMR line shapes of zeolite-adsorbate complexes:: An independent measure of solid acid strength [J].

Ehresmann, JO ;

Wang, W ;

Herreros, B ;

Luigi, DP ;

Venkatraman, TN ;

Song, WG ;

Nicholas, JB ;

Haw, JF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (36) :10868-10874

[8] PECULIARITIES OBSERVED IN H-D EXCHANGE BETWEEN PERDEUTERIOISOBUTANE AND H-ZEOLITES [J].

ENGELHARDT, J ;

HALL, WK .

JOURNAL OF CATALYSIS, 1995, 151 (01) :1-9

[9] Activation of small alkanes by heteropolyacids, a H/D exchange study: The key role of hydration water [J].

Essayem, N ;

Coudurier, G ;

Vedrine, JC ;

Habermacher, D ;

Sommer, J .

JOURNAL OF CATALYSIS, 1999, 183 (02) :292-299

[10] Reactivity of alkanes on zeolites: A theoretical ab initio study of the H/H exchange [J].

Esteves, PM ;

Nascimento, MAC ;

Mota, CJA .

JOURNAL OF PHYSICAL CHEMISTRY B, 1999, 103 (47) :10417-10420

← 1 2 3 4 5 →