Synthesis and reactivity of indenyl ruthenium(II) complexes containing the labile ligand 1,5-cyclooctadiene (COD):: Catalytic activity of [Ru(η5-C9H7)Cl(COD)]

被引:66
作者
Alvarez, P
Gimeno, J [1 ]
Lastra, E
García-Granda, S
Van der Maelen, JF
Bassetti, M
机构
[1] Univ Oviedo, Dept Quim Organ & Inorgan, Fac Quim, Inst Quim Enrique Moles,Unidad Asociada CSIC, E-33006 Oviedo, Spain
[2] Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, E-33006 Oviedo, Spain
[3] Univ Roma La Sapienza, Ctr Studio Meccanismi Reaz, CNR, Dipartimento Chim, I-00185 Rome, Italy
关键词
D O I
10.1021/om010205w
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The treatment of [RuCl2(COD)](n) with KC9H7 in THF leads to the formation of [Ru(eta (5)-C9H7)Cl(COD)] (1) (80% yield) in a one-pot synthesis. Complex 1 is also formed by the reaction of [RuCl2(COD)](n) with NaC9H7 in THF followed by treatment of the intermediate complex [Ru(eta (5)-C9H7)(eta (2)-eta (3)-C8H11)] (2) with HCL Substitution of the labile COD ligand by bulky phosphines PR3 (R = Cy, Pr-i(3)) can be achieved at room temperature in THF to give 16-electron species [Ru(eta (5)-C9H7)Cl(PR3)], which react with CO (1 atm) to afford complexes [Ru(eta (5)-C9H7)Cl(CO)(PR3)] (R = Cy (3a), Pr-i (3b)). Chelate complexes [Ru(eta (5)-C9H7)Cl{(kappa (2)-P,N)-o-Ph2PC6H4C(H)=(NBu)-Bu-t}] (4) and [Ru(eta (4)-C9H7){kappa (1)-(P)-Ph2PCH2C(O)Bu-t}{kappa (2)-(P,O)Ph2PCH= C(O)Bu-t}] (5) have been similarly prepared by reaction with the bidentate ligands. [Ru(eta (5)-C9H7)Cl(NBD)] (NBD = norbornadiene) (6) has been prepared through an exchange reaction of 1 with NBD and characterized by X-ray diffraction. Neutral complexes [Ru(eta (5)-C9H7)X-(COD)] (X = FBF3 (7), N-3 (8)) were prepared from complex 1 by metathesis reactions of the chloride ligand by AgBF4 and NaN3 respectively. The treatment of 7 in CH2Cl2 with an excess of pyridine and acetonitrile gives cationic complexes [Ru(eta (5)-C9H7)(COD)L] [BF4] in good yield (L = py (9), CH3CN (10)). The structure of complex 9 has been determined by X-ray diffraction. Complex 1 catalyzes [2+2] and [4+2] cycloaddition reactions of norbornene and 1,5-cyclooctadiene with alkynes to give exotricyclic [4.2.1.0] coupling products and exotricyclo [4.2.2.0]dec-7-enes, respectively. These processes take place with high efficiency and selectivity. Complex I is also active in the catalytic hydration of terminal alkynes to afford ketones in high yield and selectivity.
引用
收藏
页码:3762 / 3771
页数:10
相关论文
共 96 条
  • [31] Synthesis of ruthenium(II) 1,2,3-trimethylindenyl complexes: X-ray crystal structure of [Ru(=C=C=CPh2)(eta(5)-1,2,3-Me3C9H4)(CO)(PPh3)][BF4]
    Gamasa, MP
    Gimeno, J
    GonzalezBernardo, C
    Borge, J
    GarciaGranda, S
    [J]. ORGANOMETALLICS, 1997, 16 (12) : 2483 - 2485
  • [32] Phosphine substitution in indenyl- and cyclopentadienylruthenium complexes. Effect of the eta(5) ligand in a dissociative pathway
    Gamasa, MP
    Gimeno, J
    GonzalezBernardo, C
    MartinVaca, BM
    Monti, D
    Bassetti, M
    [J]. ORGANOMETALLICS, 1996, 15 (01) : 302 - 308
  • [33] Ruthenium tris(pyrazolyl)borate complexes .1. Synthesis and reactivity of Ru(HB(pz)(3))(COD)X (X=Cl, Br) and Ru(HB(pz)(3))(L(2))Cl (L=nitrogen and phosphorus donor ligands)
    Gemel, C
    Trimmel, G
    Slugovc, C
    Kremel, S
    Mereiter, K
    Schmid, R
    Kirchner, K
    [J]. ORGANOMETALLICS, 1996, 15 (19) : 3998 - 4004
  • [34] Synthesis and reactivity of [Ru{HB(pz)(3)}{P(C6H11)(3)}Cl(OCH2R)] (pz equals pyrazolyl, R=H or Me)
    Gemel, C
    Kickelbick, G
    Schmid, R
    Kirchner, K
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1997, (12): : 2113 - 2117
  • [35] RHODIUM IMINOPHOSPHINE COMPLEXES AS EFFICACIOUS OXYGEN CARRIERS - CRYSTAL-STRUCTURE OF A REPRESENTATIVE DIOXYGEN ADDUCT
    GHILARDI, CA
    MIDOLLINI, S
    MONETI, S
    ORLANDINI, A
    SCAPACCI, G
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (23): : 3371 - 3376
  • [36] GIMENO J, UNPUB
  • [37] ANALYSIS OF SINGLE-CRYSTAL BRAGG-REFLECTIONS FROM PROFILE MEASUREMENTS
    GRANT, DF
    GABE, EJ
    [J]. JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1978, 11 (APR) : 114 - 120
  • [38] HALL SR, 1995, XTAL GX PACKAGE MANU
  • [39] FORMATION AND PROPERTIES OF SOME CHLORACARBONYL COMPLEXES OF RUTHENIUM (2) AND RUTHENIUM(3)
    HALPERN, J
    JAMES, BR
    KEMP, ALW
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (22) : 5142 - &
  • [40] CATALYSIS OF HYDRATION OF ACETYLENIC COMPOUNDS BY RUTHENIUM(III) CHLORIDE
    HALPERN, J
    JAMES, BR
    KEMP, ALW
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (19) : 4097 - &