SINGLET METHYLENE AND HALOCARBENES INSERTIONS INTO POLAR N–H BONDS OF AMINES-Reference-Cited by-同舟云学术

SINGLET METHYLENE AND HALOCARBENES INSERTIONS INTO POLAR N–H BONDS OF AMINES

Published:2009-12 Issue:06 Volume:08 Page:1143-1153
ISSN:0219-6336
Container-title:Journal of Theoretical and Computational Chemistry
language:en
Short-container-title:J. Theor. Comput. Chem.

Author:

RAMASAMI K.¹,RAMALINGAM M.²,VENUVANALINGAM P.³

Affiliation:

1. Department of Chemistry, Nehru Memorial College, Puthanampatti, 621007, India

2. CRD, PRIST University, Vallam, Thanjavur, 613403, India

3. School of Chemistry, Bharathidasan University, Tiruchirapalli, 620024, India

Abstract

The insertion of singlet 1CH2 , 1CHF , and 1CF2 into polar N–H bonds of RNH2 ( R = –CH3, –C2H5, –C3H7 or –CH(CH3)2 ) has been investigated at HF, MP2, and DFT levels using 6-31g (d, p) basis set. The insertions proceed via a two-step mechanism. The potential energy surface exploration identifies an ylide formation followed by the 1,2-proton shift concertedly giving the secondary amine. The barrier height varies with the type of carbene and amine. HOMO of amines and LUMO of carbenes control the initial interactions and it is confirmed by NBO charge analysis.

Publisher

World Scientific Pub Co Pte Lt

Subject

Computational Theory and Mathematics,Physical and Theoretical Chemistry,Computer Science Applications

Link

https://www.worldscientific.com/doi/pdf/10.1142/S0219633609005398

Reference30 articles.

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2. Transition states and charge analyses along the IRC for the singlet chlorocarbenes insertions into C–H bond of alkanes

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