By: Ramasami, K (Ramasami, K.) [ 2 ] ; Ramalingam, M (Ramalingam, M.) [ 1 ] ; Venuvanalingam,
P (Venuvanalingam, P.) [ 3 ]
JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY
Volume: 8
Issue: 6
Pages: 1143-1153
DOI: 10.1142/S0219633609005398
Published: DEC 2009
View Journal Information
The insertion of singlet (1)CH(2), (1)CHF, and (1)CF(2) into polar N-H bonds of RNH(2) (R = -CH(3), -
C(2)H(5), -C(3)H(7) or -CH(CH(3))(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.
Author Keywords: N-H insertions ; halocarbenes ; ab initio ; density functional theory (DFT) ; NBO
KeyWords Plus: DENSITY-FUNCTIONAL THERMOCHEMISTRY ; ALIPHATIC DIAZO-
COMPOUNDS ; LASER FLASH-PHOTOLYSIS ; TRANSITION-STATES ; EXACT-
EXCHANGE ; YLIDES ; DECOMPOSITION ; ENERGETICS
Reprint Address: Ramalingam, M (reprint author)
PRIST Univ, CRD, Vallam 613403, Vallam, India.
Addresses:
[ 1 ] PRIST Univ, CRD, Vallam 613403, Vallam, India
[ 2 ] Nehru Mem Coll, Dept Chem, Puthanampatti 621007, India
[ 3 ] Bharathidasan Univ, Sch Chem, Tiruchchirappalli 6200024, Tamil Nadu, India
E-mail Addresses: km_ramalingam@yahoo.co.in
WORLD SCIENTIFIC PUBL CO PTE LTD, 5 TOH TUCK LINK, SINGAPORE 596224, SINGAPORE

Research Areas: Chemistry
Web of Science Categories: Chemistry, Multidisciplinary
Document Type: Article
Language: English
Accession Number: WOS:000274425700004
ISSN: 0219-6336
IDS Number: 554HI
Cited References in Web of Science Core Collection: 31
Times Cited in Web of Science Core Collection: 1