Experimental and theoretical studies on the course of CO insertion into Pt-C and Pd-C bonds in neutral and cationic complexes, [MR(Cl){P(CH3)3}2] and [MR{P(CH3)3}2(s)]+BF 4 - (M=Pt, Pd, R=CH3, C6H5, s=coordinated solvent)

Yoshihito Kayaki, Hirokazu Tsukamoto, Masaki Kaneko, Isao Shimizu, Akio Yamamoto, Masanori Tachikawa, Takahito Nakajima

    Research output: Contribution to journalArticle

    26 Citations (Scopus)

    Abstract

    Behavior of neutral and cationic cis- and trans-monoorganoplatinum complexes has been examined and compared with that of the corresponding monoorganopalladium complexes. The cis- and trans-monoorganoplatinum complexes having two trimethylphosphine ligands, [PtR(acetone){P(CH3)3}2]+BF 4 - (R=CH3 and C6H5) (4 and 5), have been prepared by removal of the chloride ligand in neutral complexes, [PdR(Cl){P(CH3)3}2] (2 and 3) with one equivalent of AgBF4. The cationic platinum complexes retaining the cis configuration of the parent neutral complexes, when prepared at low temperature, were found to be isomerized into the trans complexes 5 above -10°C for the methyl complex 5a and above -30°C for the phenyl complex 5b. Treatment of the cationic complexes 4 and 5 with CO gave no CO insertion product but afforded only the CO-coordinated trans-monoorganoplatinum complexes. The reluctance of the organoplatinum complexes toward CO insertion stands in contrast with the ease for the CO insertion of the corresponding organopalladium complexes. For clarifying the reasons of the marked difference between the behavior of the two Group 10 metal complexes the ab initio molecular orbital calculations with the MP2 level have been performed. We have found the transition states for the cis to trans isomerization of the three-coordinated cationic monoalkylplatinum complexes and for the CO insertion into the Pt-CH3 bond. The calculated barriers for the isomerization and CO insertion in the cationic organoplatinum complex are higher than those for the corresponding organopalladium complex in agreement with the experimental results showing the poor reactivity of the solvent-coordinated cationic organoplatinum complexes toward CO insertion compared to the organopalladium complexes. The reason for the difference in the reactivity between the palladium and platinum complexes can be ascribed to the relativistic effect of the platinum complexes.

    Original languageEnglish
    Pages (from-to)199-209
    Number of pages11
    JournalJournal of Organometallic Chemistry
    Volume622
    Issue number1-2
    DOIs
    Publication statusPublished - 2001 Mar 9

    Fingerprint

    Carbon Monoxide
    Platinum
    insertion
    Theoretical Models
    Isomerization
    Ligands
    Orbital calculations
    platinum
    Molecular orbitals
    Metal complexes
    Acetone
    Palladium
    isomerization
    reactivity
    reluctance
    ligands
    relativistic effects
    retaining
    acetone
    palladium

    Keywords

    • Ab initio calculations
    • Cis-trans isomerization
    • CO insertion
    • Monoalkyl complexes
    • Palladium
    • Platinum

    ASJC Scopus subject areas

    • Biochemistry
    • Inorganic Chemistry
    • Organic Chemistry
    • Physical and Theoretical Chemistry
    • Materials Chemistry

    Cite this

    Experimental and theoretical studies on the course of CO insertion into Pt-C and Pd-C bonds in neutral and cationic complexes, [MR(Cl){P(CH3)3}2] and [MR{P(CH3)3}2(s)]+BF 4 - (M=Pt, Pd, R=CH3, C6H5, s=coordinated solvent). / Kayaki, Yoshihito; Tsukamoto, Hirokazu; Kaneko, Masaki; Shimizu, Isao; Yamamoto, Akio; Tachikawa, Masanori; Nakajima, Takahito.

    In: Journal of Organometallic Chemistry, Vol. 622, No. 1-2, 09.03.2001, p. 199-209.

    Research output: Contribution to journalArticle

    Kayaki, Yoshihito ; Tsukamoto, Hirokazu ; Kaneko, Masaki ; Shimizu, Isao ; Yamamoto, Akio ; Tachikawa, Masanori ; Nakajima, Takahito. / Experimental and theoretical studies on the course of CO insertion into Pt-C and Pd-C bonds in neutral and cationic complexes, [MR(Cl){P(CH3)3}2] and [MR{P(CH3)3}2(s)]+BF 4 - (M=Pt, Pd, R=CH3, C6H5, s=coordinated solvent). In: Journal of Organometallic Chemistry. 2001 ; Vol. 622, No. 1-2. pp. 199-209.
    @article{2ac6439f949c4724b4488684fa192189,
    title = "Experimental and theoretical studies on the course of CO insertion into Pt-C and Pd-C bonds in neutral and cationic complexes, [MR(Cl){P(CH3)3}2] and [MR{P(CH3)3}2(s)]+BF 4 - (M=Pt, Pd, R=CH3, C6H5, s=coordinated solvent)",
    abstract = "Behavior of neutral and cationic cis- and trans-monoorganoplatinum complexes has been examined and compared with that of the corresponding monoorganopalladium complexes. The cis- and trans-monoorganoplatinum complexes having two trimethylphosphine ligands, [PtR(acetone){P(CH3)3}2]+BF 4 - (R=CH3 and C6H5) (4 and 5), have been prepared by removal of the chloride ligand in neutral complexes, [PdR(Cl){P(CH3)3}2] (2 and 3) with one equivalent of AgBF4. The cationic platinum complexes retaining the cis configuration of the parent neutral complexes, when prepared at low temperature, were found to be isomerized into the trans complexes 5 above -10°C for the methyl complex 5a and above -30°C for the phenyl complex 5b. Treatment of the cationic complexes 4 and 5 with CO gave no CO insertion product but afforded only the CO-coordinated trans-monoorganoplatinum complexes. The reluctance of the organoplatinum complexes toward CO insertion stands in contrast with the ease for the CO insertion of the corresponding organopalladium complexes. For clarifying the reasons of the marked difference between the behavior of the two Group 10 metal complexes the ab initio molecular orbital calculations with the MP2 level have been performed. We have found the transition states for the cis to trans isomerization of the three-coordinated cationic monoalkylplatinum complexes and for the CO insertion into the Pt-CH3 bond. The calculated barriers for the isomerization and CO insertion in the cationic organoplatinum complex are higher than those for the corresponding organopalladium complex in agreement with the experimental results showing the poor reactivity of the solvent-coordinated cationic organoplatinum complexes toward CO insertion compared to the organopalladium complexes. The reason for the difference in the reactivity between the palladium and platinum complexes can be ascribed to the relativistic effect of the platinum complexes.",
    keywords = "Ab initio calculations, Cis-trans isomerization, CO insertion, Monoalkyl complexes, Palladium, Platinum",
    author = "Yoshihito Kayaki and Hirokazu Tsukamoto and Masaki Kaneko and Isao Shimizu and Akio Yamamoto and Masanori Tachikawa and Takahito Nakajima",
    year = "2001",
    month = "3",
    day = "9",
    doi = "10.1016/S0022-328X(00)00916-5",
    language = "English",
    volume = "622",
    pages = "199--209",
    journal = "Journal of Organometallic Chemistry",
    issn = "0022-328X",
    publisher = "Elsevier",
    number = "1-2",

    }

    TY - JOUR

    T1 - Experimental and theoretical studies on the course of CO insertion into Pt-C and Pd-C bonds in neutral and cationic complexes, [MR(Cl){P(CH3)3}2] and [MR{P(CH3)3}2(s)]+BF 4 - (M=Pt, Pd, R=CH3, C6H5, s=coordinated solvent)

    AU - Kayaki, Yoshihito

    AU - Tsukamoto, Hirokazu

    AU - Kaneko, Masaki

    AU - Shimizu, Isao

    AU - Yamamoto, Akio

    AU - Tachikawa, Masanori

    AU - Nakajima, Takahito

    PY - 2001/3/9

    Y1 - 2001/3/9

    N2 - Behavior of neutral and cationic cis- and trans-monoorganoplatinum complexes has been examined and compared with that of the corresponding monoorganopalladium complexes. The cis- and trans-monoorganoplatinum complexes having two trimethylphosphine ligands, [PtR(acetone){P(CH3)3}2]+BF 4 - (R=CH3 and C6H5) (4 and 5), have been prepared by removal of the chloride ligand in neutral complexes, [PdR(Cl){P(CH3)3}2] (2 and 3) with one equivalent of AgBF4. The cationic platinum complexes retaining the cis configuration of the parent neutral complexes, when prepared at low temperature, were found to be isomerized into the trans complexes 5 above -10°C for the methyl complex 5a and above -30°C for the phenyl complex 5b. Treatment of the cationic complexes 4 and 5 with CO gave no CO insertion product but afforded only the CO-coordinated trans-monoorganoplatinum complexes. The reluctance of the organoplatinum complexes toward CO insertion stands in contrast with the ease for the CO insertion of the corresponding organopalladium complexes. For clarifying the reasons of the marked difference between the behavior of the two Group 10 metal complexes the ab initio molecular orbital calculations with the MP2 level have been performed. We have found the transition states for the cis to trans isomerization of the three-coordinated cationic monoalkylplatinum complexes and for the CO insertion into the Pt-CH3 bond. The calculated barriers for the isomerization and CO insertion in the cationic organoplatinum complex are higher than those for the corresponding organopalladium complex in agreement with the experimental results showing the poor reactivity of the solvent-coordinated cationic organoplatinum complexes toward CO insertion compared to the organopalladium complexes. The reason for the difference in the reactivity between the palladium and platinum complexes can be ascribed to the relativistic effect of the platinum complexes.

    AB - Behavior of neutral and cationic cis- and trans-monoorganoplatinum complexes has been examined and compared with that of the corresponding monoorganopalladium complexes. The cis- and trans-monoorganoplatinum complexes having two trimethylphosphine ligands, [PtR(acetone){P(CH3)3}2]+BF 4 - (R=CH3 and C6H5) (4 and 5), have been prepared by removal of the chloride ligand in neutral complexes, [PdR(Cl){P(CH3)3}2] (2 and 3) with one equivalent of AgBF4. The cationic platinum complexes retaining the cis configuration of the parent neutral complexes, when prepared at low temperature, were found to be isomerized into the trans complexes 5 above -10°C for the methyl complex 5a and above -30°C for the phenyl complex 5b. Treatment of the cationic complexes 4 and 5 with CO gave no CO insertion product but afforded only the CO-coordinated trans-monoorganoplatinum complexes. The reluctance of the organoplatinum complexes toward CO insertion stands in contrast with the ease for the CO insertion of the corresponding organopalladium complexes. For clarifying the reasons of the marked difference between the behavior of the two Group 10 metal complexes the ab initio molecular orbital calculations with the MP2 level have been performed. We have found the transition states for the cis to trans isomerization of the three-coordinated cationic monoalkylplatinum complexes and for the CO insertion into the Pt-CH3 bond. The calculated barriers for the isomerization and CO insertion in the cationic organoplatinum complex are higher than those for the corresponding organopalladium complex in agreement with the experimental results showing the poor reactivity of the solvent-coordinated cationic organoplatinum complexes toward CO insertion compared to the organopalladium complexes. The reason for the difference in the reactivity between the palladium and platinum complexes can be ascribed to the relativistic effect of the platinum complexes.

    KW - Ab initio calculations

    KW - Cis-trans isomerization

    KW - CO insertion

    KW - Monoalkyl complexes

    KW - Palladium

    KW - Platinum

    UR - http://www.scopus.com/inward/record.url?scp=0000050721&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=0000050721&partnerID=8YFLogxK

    U2 - 10.1016/S0022-328X(00)00916-5

    DO - 10.1016/S0022-328X(00)00916-5

    M3 - Article

    VL - 622

    SP - 199

    EP - 209

    JO - Journal of Organometallic Chemistry

    JF - Journal of Organometallic Chemistry

    SN - 0022-328X

    IS - 1-2

    ER -