Ключевые интермедиаты селективного окисления

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  • . .

    35

    .

    .,

    2000

    . .

    THE KEY INTERMEDIATES OF SELECTIVE OXIDATION

    E . P. TALZI

    The selective oxidation of hydrocarbons is ofimportance in the production of fine chemicals.The elucidation of the mechanisms of thesereactions can be helpful to improve the existingprosesses. The role of metal-oxygen interme-diates in selective catalytic oxidation isconsidered.

    - - . , - , - . - - - .

    , - , - - . , - () (ROOH). -, , - . - -. - - - .

    , - , , , , , , - (LM=O), - (LMOOR) (LMOOH)( , L ). - .

    - , . , (CrO

    2

    Cl

    2

    ), - - . .

    LM O 2( )( ),

    LM O 22( )( ),

    MnO4( )

    www.issep.rssi.ru

  • , 6 , 7 , 2 0 0 0

    36

    1995 - CrO

    2

    Cl

    2

    -, [1]. , CrO

    2

    Cl

    2

    - [Cr

    V

    (O)Cl

    2

    (OH)]. ( 1): - Cl CrO

    2

    Cl

    2

    , CrO

    2

    Cl

    2

    , - . - CrO

    2

    Cl

    2

    -, , OH

    , RO

    ROO

    . , - - OH (HOH, 119 /,

    t

    BuOH, 105 /,

    t

    BuOOH, 83 /, Cl

    2

    OCrOH, 80 /,. 1). , CrO

    2

    Cl

    2

    . , - , - -, OH, .

    , - . - - . 90- - (III)

    CrO2Cl2

    tBuOO

    tBuO

    OH

    CrO2Cl2

    tBuOO

    CrO2Cl2

    tBuOO

    tBuO

    OH

    OH

    tBuO

    75 85 105

    806

    90 100 110 120

    8010

    90 100 110 120

    115 12595D(OH), /

    D(OH), /

    D(OH), /

    5

    0

    5

    2

    2

    6

    10

    5

    0

    5

    lg k

    lg k

    lg k

    . 1.

    - OH

    ,

    t

    BuO

    ,

    t

    BuOO

    CrO

    2

    Cl

    2

    (

    a

    ), (

    ) (

    ) -

    CrO2Cl2 + CrCl OH

    O

    Cl

    Cl

    O

    OCl

    OCO2Cr CO2Cr

    ka

    ke

    kO2

    CrO2Cl2

    kCl

    +

    OCr

    CrO2Cl2CrO2Cl2 kO

    1.

    CrO

    2

    Cl

    2

  • . .

    37

    ( 1,2), - - [2]., - Mn(V), Mn(V)=O - Mn(III) c (NaOCl, IOPh). Mn(V) - , . - (V) - (3), Cr(V)=O. -, .

    . - , - :

    RH + O

    2

    + 2H

    +

    + 2e ROH + H

    2

    O

    , - - - . , , , Fe(IV)=O.

    O

    Mn

    N

    O

    N

    Cl

    tButBu

    tButBu

    O

    Mn

    N

    O

    N

    H

    H

    Ph

    Ph

    +

    PF6

    1

    2

    +

    O

    Cr

    N

    O

    NORR

    3

    P-450. P-450 - , . - - - (P-450Fe(V)=O) - P-450. - -, , , , . (P

    +

    Fe(IV)=O) - - - (P

    +

    -- - ).

    - . - , - LFe(V)=O (RH) LFe(IV)OH R

    . c - LFe(III) ROH. , .. .. [3], - - - .

    , -

    - Ni(II), Zn(II), Co(III), Fe(III), Ce(III), Ti(IV),Th(IV), Hf(IV), Zr(IV), Sn(IV), V(V), Nb(V), Mo(VI). - . - , . in situ LCo(III) - . , , - - (, , ).

    O2 .

    O2( )

  • , 6 , 7 , 2 0 0 0

    38

    - H KO

    2

    c , , , -, (II). [4].

    (I II). I , II . I , - II -. , I II -- (

    1

    - I,

    2

    II). - - .

    . 2 - I ([Pd

    3

    (HCO

    2

    )

    5

    (O

    2

    )]) II([Pd(HCO

    2

    )(O

    2

    )]. --.

    - - . - , - . - . , - . - . , - , , - . - - . - .

    . , , - -, , . 1970 MoO(O

    2

    )

    2

    HMPA, HMPA , , - . - - MoO(O

    2

    )L

    n

    , (4) MoO(O

    2

    )

    2

    L

    1

    L

    2

    (5) - (L

    n

    , L

    1

    , L

    2

    ) , - .

    -

    17

    O,

    95

    Mo MoO(O

    2

    )

    2

    H

    2

    O MoO(O

    2

    )

    2

    (H

    2

    O)

    2

    - oO

    3

    + HOOH . , MoO(O

    2

    )

    2

    H

    2

    O

    MoL

    L O

    OO

    L L

    MoO

    O O

    OO

    L1 L24 5

    Pd(2)

    1,801

    Pd(1)

    117

    Pd(3)

    1,384

    125 59

    Pd

    H

    C

    O O

    1,451

    1,804

    2,231

    1,251

    [Pd3(HCO2)5(O2)]

    [Pd(HCO2)(O2)]

    OC

    HO

    . 2.

    - I (

    1

    -) II (

    2

    - ). - O2

    O2

    I

    II

  • . .

    39

    , - MoO(O

    2

    )

    2

    (H

    2

    O)

    2

    .

    - . -, - , , , , , - - . , - - , -, , - - . - , VO(O

    2

    )(Pic)(H

    2

    O)

    2

    , Pic -, . .

    , - , - - , , . - - - . , - . - i(OEt)

    2

    (O

    2

    )

    1

    Ti(OEt)

    4

    c HOOH .

    , - - (ROOH) , -, . - -

    .

    - ,

    , iCl

    4

    . - - , - .

    1

    13

    - - - (

    1

    2

    ) (. 3).

    -

    95

    ,

    51

    V,

    17

    O -, VO(acac)

    2

    + tBuOOH MoO2(acac)2 + tBuOOH (acac-). , VO(acac)2(OOtBu) MoO2(OOtBu)2 . , -. - VO(OOtBu)2(OtBu) VO(OOtBu)(OtBu)2 . - oO2(1,2-diolo)(OOtBu), 1,2-diolo--- [4].

    - - . (BLM) , . (II) . - - (III) FeBLM(OOH) (. 4).

    N

    OCO

    O

    VOOMe

    Me

    Me

    C

    O

    H H

    O CO

    TiO

    tBuOO

    O

    OO

    N

    Ti

    OOtBu

    OO

    N

  • , 6 , 7 , 2 0 0 040

    FeBLM(OOH) - 2 6, = 7,0. . FeBLM(OOH) - 50% Fe-BLM(OOH). , - FeBLM(OOH) , , - , FeBLM (-).

    -. . -

    . -, [4], . 5. 10 11. , , FeBLM(OOH). , (, -) 10 11. - .

    , - . - - . - .

    , -, - . , , - , ,

    . 3. 1 13 -

    NNFe(III)

    NH2

    OOH

    N N

    N

    H

    N

    O

    H

    O

    N

    CH3H2N

    H

    H NH2

    O

    H

    O

    H2N

    H

    H

    . 4. . -

    N

    O

    O

    Ti

    OR

    OtBu

    O

    L

    O

    O

    R = iPr, L = iPrOHR = tBu, L = iPrOHR = tBu, L

    R = Me tBu, R1 = tBu: 1R = Me tBu, R1 = iPr, Et OtBu: 1 2

    Ti(2OOtBu)n(OR)4 nR = iPr, n = 1, 2, 3, 4R = tBu, n = 1, 2, 3R = Et, n = 3

    TiOR1

    OOtBu

    O

    O

    O

    O

    R

    R

    R

    R

    TiO

    O

    O

    O

    O

    O O

    OOtBuTi

    OTi

    OOiPr

    OiPr

    OiPriPrOiPrO

    OtBuO

    iPr

    iPr

    TiO

    TiO

    iPrOiPrO

    OtBuO

    OiPrOiPr

    OtBuO

    iPr

    iPr

  • . . 41

    .

    1. Cook G.K., Mayer J.M. // J. Amer. Chem. Soc. 1995. Vol. 117.P. 71397156.

    2. Dalton C.T., Ryan K.M., Wall V.M. et al. // Topics in Catalysis.1998. Vol. 5. P. 7591.

    3. .., .., .., ..// . 1998. . 67, . 4. . 376398.

    4. Talsi E.P. // New J. Chem. 1997. Vol. 21. P. 709725.

    ..

    * * *

    , ,, . - . .. . - - - - . 50 .

    NH N

    HNN

    N

    NH

    HN

    N

    CH NCH2

    CH2

    N

    N

    N

    N

    N

    N

    NN

    N N

    N N

    Fe(TPP)OOH TPP

    Fe(cycld)OOH cycld

    Fe(4NPy)OOH 4NPy

    Fe(TPA)OOH TPA

    Fe(bpy)2(Py)OOH bpy

    Fe(phen)2(Py)OOH phen

    6

    7

    811

    9

    10

    . 5. ,