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

Hiromi Nakai, Sumihito Fukada, Hiroshi Nakatsuji

    Research output: Contribution to journalArticle

    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 languageEnglish
    Pages (from-to)973-980
    Number of pages8
    JournalJournal of Physical Chemistry A
    Volume101
    Issue number6
    Publication statusPublished - 1997 Feb 6

    Fingerprint

    Photoisomerization
    Isomerization
    Platinum
    Excited states
    isomerization
    platinum
    Decomposition
    Acetylene
    Ground state
    excitation
    decomposition
    planar structures
    Association reactions
    acetylene
    configuration interaction
    atomic energy levels
    Geometry
    ground state
    products
    geometry

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

    Cite this

    Theoretical study on the thermal and photochemical isomerization reactions of dicyanoacetylene complex of platinum Pt(PH3)2(C4N2). / Nakai, Hiromi; Fukada, Sumihito; Nakatsuji, Hiroshi.

    In: Journal of Physical Chemistry A, Vol. 101, No. 6, 06.02.1997, p. 973-980.

    Research output: Contribution to journalArticle

    @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 = "2",
    day = "6",
    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

    M3 - Article

    VL - 101

    SP - 973

    EP - 980

    JO - Journal of Physical Chemistry A

    JF - Journal of Physical Chemistry A

    SN - 1089-5639

    IS - 6

    ER -