SURFACE ORGANOMETALLIC CHEMISTRY - REACTION OF TRIS-ALLYL RHODIUM WITH SURFACES OF SILICA, ALUMINA, TITANIA, AND MAGNESIA

被引:65
作者
DUFOUR, P
HOUTMAN, C
SANTINI, CC
NEDEZ, C
BASSET, JM
HSU, LY
SHORE, SG
机构
[1] UNIV CLAUDE BERNARD, INST RECH CATALYSE, CONVENT, 2 AVE A EINSTEIN, F-69626 VILLEURBANNE, FRANCE
[2] ECOLE SUPER CHIM IND LYON, F-69621 VILLEURBANNE, FRANCE
[3] OHIO STATE UNIV, DEPT CHEM, COLUMBUS, OH 43210 USA
关键词
D O I
10.1021/ja00037a031
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction of Rh(eta-3-C3H5)3, 1, with silica, alumina, titania, and magnesia has been followed by infrared spectroscopy, isotopic labeling experiments, quantitative analysis of gaseous products, and elemental analysis. Complex 1 reacts rapidly with alumina pretreated to 350-degrees-C and with silica and titania to form a bis-allylic rhodium species grafted to the surface, but no immediate reaction was observed between 1 and alumina pretreated to 200-degrees-C or magnesia. This reaction likely proceeds via electrophilic cleavage of Rh-C bonds of 1 by a surface OH group. On silica, the results of IR experiments after labeling the surface with O-16-D and O-18-H and structural arguments suggest that two 18-electron species are possible on the surface: one for which the rhodium is coordinated both to an oxygen and a hydroxyl group linked to the same silicon atom and another for which the oxygen atom and the OH group are linked to two different silicon atoms. Molecular mechanics modeling of silica, alumina, and titania was used as a complement to the experimental work to test the plausibility of various modes of attachment of the rhodium allyl complex.
引用
收藏
页码:4248 / 4257
页数:10
相关论文
共 52 条
  • [41] Sinfelt J.H., 1973, ADV CATAL, V23, P91
  • [42] INVESTIGATION OF A MODEL CATALYTIC-SYSTEM IN ULTRAHIGH-VACUUM - THE ADSORPTION OF TRIALLYLRHODIUM ON THE TIO2 (001) SURFACE
    SMITH, PB
    BERNASEK, SL
    SCHWARTZ, J
    MCNULTY, GS
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (18) : 5654 - 5655
  • [43] THE ADSORPTION OF WATER ON TIO2(001)
    SMITH, PB
    BERNASEK, SL
    [J]. SURFACE SCIENCE, 1987, 188 (1-2) : 241 - 254
  • [44] CRYSTAL-STRUCTURES OF (1,5-CYCLOOCTADIENE)DI-MU-METHOXO-DIRHODIUM(I) AND TETRAKIS(ETA-3-ALLYL)DI-MU-HYDROXO-DIRHODIUM(III)
    TANAKA, I
    JINNO, N
    KUSHIDA, T
    TSUTSUI, N
    ASHIDA, T
    SUZUKI, H
    SAKURAI, H
    MOROOKA, Y
    IKAWA, T
    [J]. BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1983, 56 (03) : 657 - 661
  • [45] SURFACE SUPPORTED METAL CLUSTER CARBONYLS - CHEMISORPTION DECOMPOSITION AND REACTIVITY OF RH4(CO)12 SUPPORTED ON SILICA AND ALUMINA
    THEOLIER, A
    SMITH, AK
    LECONTE, M
    BASSET, JM
    ZANDERIGHI, GM
    PSARO, R
    UGO, R
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1980, 191 (02) : 415 - 424
  • [46] THEORY OF ELECTRONIC-STRUCTURE OF OXIDE SURFACES
    TSUKADA, M
    ADACHI, H
    SATOKO, C
    [J]. PROGRESS IN SURFACE SCIENCE, 1983, 14 (02) : 113 - 173
  • [47] INFRARED STUDY OF SILICA-GEL SURFACE .1. DRY SILICA-GEL
    VANROOSMALEN, AJ
    MOL, JC
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1978, 82 (25) : 2748 - 2751
  • [48] CATALYTICALLY ACTIVE METAL OXIDE-SUPPORTED RHODIUM HYDRIDE COMPLEXES
    WARD, MD
    SCHWARTZ, J
    [J]. JOURNAL OF MOLECULAR CATALYSIS, 1981, 11 (2-3): : 397 - 407
  • [49] SYNTHESIS AND PARTIAL CHARACTERIZATION OF (SILICA)RHODIUM DIHYDRIDES - A NEW CATALYST FOR OLEFIN HYDROGENATION
    WARD, MD
    HARRIS, TV
    SCHWARTZ, J
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1980, (08) : 357 - 359
  • [50] WARD MD, 1981, THESIS PRINCETON U