Hydroxycarbene: Watching a molecular mole at work

被引：15

作者：

Bucher, Goetz ^{[1
]}

机构：

[1] Univ Glasgow, Glasgow G12 8QQ, Lanark, Scotland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2008年 / 47卷 / 37期

关键词：

carbenes; matrix isolation; quantum chemistry; reactive intermediates; tunnel effect;

D O I：

10.1002/anie.200803195

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Finding a pico-mole: like a mole, hydroxycarbene prefers to tunnel through barriers. Generated from glyoxylic acid by pyrolysis, H-C-OH rearranges to formaldehyde within two hours even in solid argon at T = 10 K. This behavior is best rationalized by quantum mechanical tunneling. (Figure Presented) © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

收藏

页码：6957 / 6958

页数：2

相关论文

共 9 条

[1] A STABLE CRYSTALLINE CARBENE [J].

ARDUENGO, AJ ;

HARLOW, RL ;

KLINE, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (01) :361-363

[2] PHENOXYCHLOROCARBENE - SPECTROSCOPY AND PHOTOCHEMICAL INTERCONVERSION OF GEOMETRIC ISOMERS [J].

KESSELMAYER, MA ;

SHERIDAN, RS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (04) :844-845

[3] Cyclopropenylidenes: From interstellar space to an isolated derivative in the laboratory [J].

Lavallo, V ;

Canac, Y ;

Donnadieu, B ;

Schoeller, WW ;

Bertrand, G .

SCIENCE, 2006, 312 (5774) :722-724

[4] PHENOXYCHLOROCARBENE, A 2ND AMBIPHILE [J].

MOSS, RA ;

PEREZ, LA ;

WLOSTOWSKA, J ;

GUO, W ;

KROGHJESPERSEN, K .

JOURNAL OF ORGANIC CHEMISTRY, 1982, 47 (22) :4177-4180

[5] VINYLIDENE - A VERY SHALLOW MINIMUM ON THE C2H2 POTENTIAL-ENERGY SURFACE - STATIC AND DYNAMICAL CONSIDERATIONS [J].

OSAMURA, Y ;

SCHAEFER, HF ;

GRAY, SK ;

MILLER, WH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (08) :1904-1907

[6] Physical chemistry -: Cool it, baby [J].

Rasanen, Markku .

NATURE, 2008, 453 (7197) :862-863

[7] Capture of hydroxymethylene and its fast disappearance through tunnelling [J].

Schreiner, Peter R. ;

Reisenauer, Hans Peter ;

Pickard, Frank C. ;

Simmonett, Andrew C. ;

Allen, Wesley D. ;

Matyus, Edit ;

Csaszar, Attila G. .

NATURE, 2008, 453 (7197) :906-U42

[8]

SCHREINER PR, 2008, ANGEW CHEM INT ED, V47

[9]

SCHREINER PR, 2008, ANGEW CHEM, V120