Theoretical study on the thermal and photochemical isomerization reactions of dicyanoacetylene complex of platinum Pt(PH3)2(C4N2)

Hiromi Nakai; Sumihito Fukada; Hiroshi Nakatsuji

doi:10.1021/jp960830s

Theoretical study on the thermal and photochemical isomerization reactions of dicyanoacetylene complex of platinum Pt(PH₃)₂(C₄N₂)

Hiromi Nakai, Sumihito Fukada, Hiroshi Nakatsuji^*

^*Corresponding author for this work

School of Advanced Science and Engineering

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

4 Citations (Scopus)

Abstract

The electronic mechanism of the photoisomerization of the dicyanoacetylene complex of platinum Pt(PH₃)₂-(C₄N₂) to the acetylide complex Pt(PH₃)₂(CN)(C≡CCN) has been investigated theoretically. The geometries of the ground and excited states are optimized by the Hartree-Fock (HF) and single excitation configuration interaction (SE-CI) methods, respectively. In the thermal process, the decomposition reaction of Pt(PH₃)₂-(C₄N₂) into Pt(PH₃)₂ and C₄N₂ occurs preferentially but the association leads to the acetylene complex rather than to the acetylide complex. The reactant, transition state, and product all have planar structures. On the other hand, in the photochemical process, the dicyanoacetylene complex is isomerized smoothly into the acetylide complex. Neither the decomposition of Pt(PH₃)₂(C₄N₂) into the neutral separated system Pt(PH₃)₂ + C₄N₂ nor that into the ionic separated systems Pt(PH₃)₂⁺ + C₄N₂^- and Pt(PH₃)₂(C₄N₂)⁺ + CN^- occurs. The intramolecular photoisomerization occurs through a bisect complex in the singlet excited state and a three-coordination Pt complex in the triplet state.

Original language	English
Pages (from-to)	973-980
Number of pages	8
Journal	Journal of Physical Chemistry A
Volume	101
Issue number	6
DOIs	https://doi.org/10.1021/jp960830s
Publication status	Published - 1997 Feb 6

ASJC Scopus subject areas

Physical and Theoretical Chemistry

Access to Document

10.1021/jp960830s

Cite this

@article{92583c2c037c47b6945ddc45ad0e645b,

title = "Theoretical study on the thermal and photochemical isomerization reactions of dicyanoacetylene complex of platinum Pt(PH3)2(C4N2)",

abstract = "The electronic mechanism of the photoisomerization of the dicyanoacetylene complex of platinum Pt(PH3)2-(C4N2) to the acetylide complex Pt(PH3)2(CN)(C≡CCN) has been investigated theoretically. The geometries of the ground and excited states are optimized by the Hartree-Fock (HF) and single excitation configuration interaction (SE-CI) methods, respectively. In the thermal process, the decomposition reaction of Pt(PH3)2-(C4N2) into Pt(PH3)2 and C4N2 occurs preferentially but the association leads to the acetylene complex rather than to the acetylide complex. The reactant, transition state, and product all have planar structures. On the other hand, in the photochemical process, the dicyanoacetylene complex is isomerized smoothly into the acetylide complex. Neither the decomposition of Pt(PH3)2(C4N2) into the neutral separated system Pt(PH3)2 + C4N2 nor that into the ionic separated systems Pt(PH3)2+ + C4N2- and Pt(PH3)2(C4N2)+ + CN- occurs. The intramolecular photoisomerization occurs through a bisect complex in the singlet excited state and a three-coordination Pt complex in the triplet state.",

author = "Hiromi Nakai and Sumihito Fukada and Hiroshi Nakatsuji",

year = "1997",

month = feb,

day = "6",

doi = "10.1021/jp960830s",

language = "English",

volume = "101",

pages = "973--980",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "6",

}

TY - JOUR

T1 - Theoretical study on the thermal and photochemical isomerization reactions of dicyanoacetylene complex of platinum Pt(PH3)2(C4N2)

AU - Nakai, Hiromi

AU - Fukada, Sumihito

AU - Nakatsuji, Hiroshi

PY - 1997/2/6

Y1 - 1997/2/6

N2 - The electronic mechanism of the photoisomerization of the dicyanoacetylene complex of platinum Pt(PH3)2-(C4N2) to the acetylide complex Pt(PH3)2(CN)(C≡CCN) has been investigated theoretically. The geometries of the ground and excited states are optimized by the Hartree-Fock (HF) and single excitation configuration interaction (SE-CI) methods, respectively. In the thermal process, the decomposition reaction of Pt(PH3)2-(C4N2) into Pt(PH3)2 and C4N2 occurs preferentially but the association leads to the acetylene complex rather than to the acetylide complex. The reactant, transition state, and product all have planar structures. On the other hand, in the photochemical process, the dicyanoacetylene complex is isomerized smoothly into the acetylide complex. Neither the decomposition of Pt(PH3)2(C4N2) into the neutral separated system Pt(PH3)2 + C4N2 nor that into the ionic separated systems Pt(PH3)2+ + C4N2- and Pt(PH3)2(C4N2)+ + CN- occurs. The intramolecular photoisomerization occurs through a bisect complex in the singlet excited state and a three-coordination Pt complex in the triplet state.

AB - The electronic mechanism of the photoisomerization of the dicyanoacetylene complex of platinum Pt(PH3)2-(C4N2) to the acetylide complex Pt(PH3)2(CN)(C≡CCN) has been investigated theoretically. The geometries of the ground and excited states are optimized by the Hartree-Fock (HF) and single excitation configuration interaction (SE-CI) methods, respectively. In the thermal process, the decomposition reaction of Pt(PH3)2-(C4N2) into Pt(PH3)2 and C4N2 occurs preferentially but the association leads to the acetylene complex rather than to the acetylide complex. The reactant, transition state, and product all have planar structures. On the other hand, in the photochemical process, the dicyanoacetylene complex is isomerized smoothly into the acetylide complex. Neither the decomposition of Pt(PH3)2(C4N2) into the neutral separated system Pt(PH3)2 + C4N2 nor that into the ionic separated systems Pt(PH3)2+ + C4N2- and Pt(PH3)2(C4N2)+ + CN- occurs. The intramolecular photoisomerization occurs through a bisect complex in the singlet excited state and a three-coordination Pt complex in the triplet state.

UR - http://www.scopus.com/inward/record.url?scp=0031555757&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0031555757&partnerID=8YFLogxK

U2 - 10.1021/jp960830s

DO - 10.1021/jp960830s

M3 - Article

AN - SCOPUS:0031555757

SN - 1089-5639

VL - 101

SP - 973

EP - 980

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 6

ER -

Theoretical study on the thermal and photochemical isomerization reactions of dicyanoacetylene complex of platinum Pt(PH₃)₂(C₄N₂)

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this