A DECEPTIVELY SIMPLE CASE OF SELECTIVE HYDROGENATION OF PHENYLACETYLENE TO STYRENE CATALYZED BY A CIS-HYDRIDO(MU-2-DIHYDROGEN)RUTHENIUM(II) COMPLEX

被引:99
作者
BIANCHINI, C
BOHANNA, C
ESTERUELAS, MA
FREDIANI, P
MELI, A
ORO, LA
PERUZZINI, M
机构
[1] UNIV ZARAGOZA,CSIC,DEPT QUIM INORGAN,INST CIENCIAS MAT ARAGON,E-50009 ZARAGOZA,SPAIN
[2] UNIV FLORENCE,DIPARTIMENTO CHIM ORGAN,I-50121 FLORENCE,ITALY
关键词
D O I
10.1021/om00059a056
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Depending on the substrate to metal complex ratio (2, 3, 4), the reaction of the cis-hydrido(eta2-dihydrogen)ruthenium(II) complex [(PP3)Ru(H)(H2)]BPh4 (2) with HC=CPh in tetrahydrofuran gives the sigma-alkenyl [(PP3)Ru{C(H)=C(H)Ph}]+ (detected spectroscopically), the sigma-alkynyl [(PP3)Ru(C=CPh)]Bph4.THF (6), or the eta3-butenynyl E-[(PP3)Ru(eta3-PhC3CHPh)}BPh4 (3a,b) {PP3 = P(CH2CH2PPh2)3]. The latter product is isolated as a 3:1 mixture of geometric isomers displaying a different anchoring mode of the butenynyl ligand to the metal center. The cis-hydride(eta3-dihydrogen)ruthenium(II) complex 2 is an active catalyst precursor for the selective hydrogenation of phenylacetate to styrene. A kinetic study carried out in 1,2-dichloroethane solution shows that the rate of the catalytic hydrogenation reaction is proportional to the initial concentration of the catalyst precursor, second order with respect to dihydrogen pressure, and independent of substrate concentration. At very low concentrations of HC=CPh (<0.12 M), the order of the catalytic rate with respect to substrate concentration tends to 1. In light of the kinetic study and of the reactivity of 2 towards HC=CPh, a reaction mechanism is proposed which essentially involves the usual cycle adopted by mono(hydrido)metal catalysts. In fact, unlike the related iron derivative [(PP3)Fe(H)(H2)]BPh4 previously investigated, dihydrogen in 2 behaves as a weakly bound ligand which is readily displaced by phenylacetylene. Other ruthenium species, namely the butenynyl complexes 3a,b and the alkynyl 6, play a significant role in the catalysis cycle as side intermediates.
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页码:3837 / 3844
页数:8
相关论文
共 33 条
  • [1] REACTIONS OF MOLECULAR-HYDROGEN COMPLEXES [RUH(ETA-2-H2)P4]BF4 WITH ALKYNES - PREPARATION AND CRYSTAL-STRUCTURE OF THE [RU(ETA-3-(PARA-TOLYL)C3CH(PARA-TOLYL))(PHP(OET)2)4]BPH4 DERIVATIVE
    ALBERTIN, G
    AMENDOLA, P
    ANTONIUTTI, S
    IANELLI, S
    PELIZZI, G
    BORDIGNON, E
    [J]. ORGANOMETALLICS, 1991, 10 (08) : 2876 - 2883
  • [2] KINETIC AND MECHANISTIC INVESTIGATION OF THE SEQUENTIAL HYDROGENATION OF PHENYLACETYLENE CATALYZED BY OSHCL(CO) (PME-TERT-BU2)2, OSHCL(CO)(P-I-PR3)2
    ANDRIOLLO, A
    ESTERUELAS, MA
    MEYER, U
    ORO, LA
    SANCHEZDELGADO, RA
    SOLA, E
    VALERO, C
    WERNER, H
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (19) : 7431 - 7437
  • [3] SIGMA-ACETYLIDE COMPLEXES OF RHODIUM(I), RHODIUM(II), AND RHODIUM(III) - CORRELATION BETWEEN ELECTROCHEMICAL (E-DEGREES') AND SPECTROSCOPIC (DELTA-NU(C=C)) PARAMETERS AND D-PI (METAL)-]PI-STAR (ACETYLIDE) TRANSFER
    BIANCHINI, C
    MELI, A
    PERUZZINI, M
    VACCA, A
    LASCHI, F
    ZANELLO, P
    OTTAVIANI, FM
    [J]. ORGANOMETALLICS, 1990, 9 (02) : 360 - 371
  • [4] CLASSICAL AND NONCLASSICAL POLYHYDRIDE RUTHENIUM(II) COMPLEXES STABILIZED BY THE TETRAPHOSPHINE P(CH2CH2PPH2)3
    BIANCHINI, C
    PEREZ, PJ
    PERUZZINI, M
    ZANOBINI, F
    VACCA, A
    [J]. INORGANIC CHEMISTRY, 1991, 30 (02) : 279 - 287
  • [5] RHODIUM COMPLEXES WITH TRIPODAL POLYPHOSPHINES AS EXCELLENT PRECURSORS TO SYSTEMS FOR THE ACTIVATION OF H-H AND C-H BONDS
    BIANCHINI, C
    MASI, D
    MELI, A
    PERUZZINI, M
    ZANOBINI, F
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (19) : 6411 - 6423
  • [6] BIANCHINI C, 1991, GAZZ CHIM ITAL, V121, P543
  • [7] A HOMOGENEOUS IRON(II) SYSTEM CAPABLE OF SELECTIVELY CATALYZING THE REDUCTION OF TERMINAL ALKYNES TO ALKENES AND BUTA-1,3-DIENES
    BIANCHINI, C
    MELI, A
    PERUZZINI, M
    VIZZA, F
    ZANOBINI, F
    FREDIANI, P
    [J]. ORGANOMETALLICS, 1989, 8 (08) : 2080 - 2082
  • [8] A RU(II) ENYNYL COMPLEX MEDIATES THE CATALYTIC DIMERIZATION OF 1-ALKYNES TO Z-1,4-DISUBSTITUTED ENYNES
    BIANCHINI, C
    PERUZZINI, M
    ZANOBINI, F
    FREDIANI, P
    ALBINATI, A
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (14) : 5453 - 5454
  • [9] SELECTIVE HYDROGENATION OF 1-ALKYNES TO ALKENES CATALYZED BY AN IRON(II) CIS-HYDRIDE ETA-2-DIHYDROGEN COMPLEX - A CASE OF INTRAMOLECULAR REACTION BETWEEN ETA-2-H-2 AND SIGMA-VINYL LIGANDS
    BIANCHINI, C
    MELI, A
    PERUZZINI, M
    FREDIANI, P
    BOHANNA, C
    ESTERUELAS, MA
    ORO, LA
    [J]. ORGANOMETALLICS, 1992, 11 (01) : 138 - 145
  • [10] AN EXCEPTIONALLY STABLE CIS-(HYDRIDE)(ETA-2-DIHYDROGEN) COMPLEX OF IRON
    BIANCHINI, C
    PERUZZINI, M
    ZANOBINI, F
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1988, 354 (02) : C19 - C22