A theoretical investigation into dimethylcarbene and its diamino and diphosphino analogs: Effects of cyclization and unsaturation on the stability and multiplicity

M. Z. Kassaee; M. Ghambarian; S. M. Musavi; F. A. Shakib; M. R. Momeni

doi:10.1002/poc.1540

A theoretical investigation into dimethylcarbene and its diamino and diphosphino analogs: Effects of cyclization and unsaturation on the stability and multiplicity

M. Z. Kassaee, M. Ghambarian, S. M. Musavi, F. A. Shakib, M. R. Momeni

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

High levels of ab initio and DFT calculations (B3LYP/6-311++ G**, B3LYP/AUG-cc-pVTZ, and CCSD(T)/6-311++G** levels) coupled with isodesmic reactions are used to compare and contrast the multiplicities and relative stabilities of singlet (s) and triplet (t) acyclic carbenes, including: dimethylcarbene, diaminocarbene, and diphosphinocarbene along with their saturated and unsaturated cyclic ones. Cyclization is unfavorable for all acyclic carbenes while unsaturation of cyclic analogs appears favorable. The simultaneous cyclization and unsaturation of dimethyl- carbene increases the singlet-triplet energy gap (δ£_s-t), while for diphosphinocarbene the situation is reversed. For diaminocarbene the increase of δE_s-t is encountered only during cyclization.

Original language	English (US)
Pages (from-to)	919-924
Number of pages	6
Journal	Journal of Physical Organic Chemistry
Volume	22
Issue number	10
DOIs	https://doi.org/10.1002/poc.1540
State	Published - Oct 2009
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry

Keywords

Ab initio
DFT
Diaminocarbene
Dimethylcarbene
Diphosphinocarbene
Isodesmic reaction
Multiplicity

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10.1002/poc.1540

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abstract = "High levels of ab initio and DFT calculations (B3LYP/6-311++ G**, B3LYP/AUG-cc-pVTZ, and CCSD(T)/6-311++G** levels) coupled with isodesmic reactions are used to compare and contrast the multiplicities and relative stabilities of singlet (s) and triplet (t) acyclic carbenes, including: dimethylcarbene, diaminocarbene, and diphosphinocarbene along with their saturated and unsaturated cyclic ones. Cyclization is unfavorable for all acyclic carbenes while unsaturation of cyclic analogs appears favorable. The simultaneous cyclization and unsaturation of dimethyl- carbene increases the singlet-triplet energy gap (δ£s-t), while for diphosphinocarbene the situation is reversed. For diaminocarbene the increase of δEs-t is encountered only during cyclization.",

keywords = "Ab initio, DFT, Diaminocarbene, Dimethylcarbene, Diphosphinocarbene, Isodesmic reaction, Multiplicity",

author = "Kassaee, {M. Z.} and M. Ghambarian and Musavi, {S. M.} and Shakib, {F. A.} and Momeni, {M. R.}",

year = "2009",

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AU - Ghambarian, M.

AU - Musavi, S. M.

AU - Shakib, F. A.

AU - Momeni, M. R.

PY - 2009/10

Y1 - 2009/10

N2 - High levels of ab initio and DFT calculations (B3LYP/6-311++ G**, B3LYP/AUG-cc-pVTZ, and CCSD(T)/6-311++G** levels) coupled with isodesmic reactions are used to compare and contrast the multiplicities and relative stabilities of singlet (s) and triplet (t) acyclic carbenes, including: dimethylcarbene, diaminocarbene, and diphosphinocarbene along with their saturated and unsaturated cyclic ones. Cyclization is unfavorable for all acyclic carbenes while unsaturation of cyclic analogs appears favorable. The simultaneous cyclization and unsaturation of dimethyl- carbene increases the singlet-triplet energy gap (δ£s-t), while for diphosphinocarbene the situation is reversed. For diaminocarbene the increase of δEs-t is encountered only during cyclization.

AB - High levels of ab initio and DFT calculations (B3LYP/6-311++ G**, B3LYP/AUG-cc-pVTZ, and CCSD(T)/6-311++G** levels) coupled with isodesmic reactions are used to compare and contrast the multiplicities and relative stabilities of singlet (s) and triplet (t) acyclic carbenes, including: dimethylcarbene, diaminocarbene, and diphosphinocarbene along with their saturated and unsaturated cyclic ones. Cyclization is unfavorable for all acyclic carbenes while unsaturation of cyclic analogs appears favorable. The simultaneous cyclization and unsaturation of dimethyl- carbene increases the singlet-triplet energy gap (δ£s-t), while for diphosphinocarbene the situation is reversed. For diaminocarbene the increase of δEs-t is encountered only during cyclization.

KW - Ab initio

KW - DFT

KW - Diaminocarbene

KW - Dimethylcarbene

KW - Diphosphinocarbene

KW - Isodesmic reaction

KW - Multiplicity

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A theoretical investigation into dimethylcarbene and its diamino and diphosphino analogs: Effects of cyclization and unsaturation on the stability and multiplicity

Abstract

All Science Journal Classification (ASJC) codes

Keywords

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