Mechanism of complex formation of ruthenium(II) aquacomplexes with H2C=CH2, MeCN, Me2SO, and CO:: Metal-water bond rupture as rate-determining step

被引:20
作者
Aebischer, N [1 ]
Churlaud, R [1 ]
Dolci, L [1 ]
Frey, U [1 ]
Merbach, AE [1 ]
机构
[1] Univ Lausanne, Inst Chim Minerale & Analyt, BCH Dorigny, CH-1015 Lausanne, Switzerland
关键词
D O I
10.1021/ic980628z
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction [Ru(H2O)(6)](2+) + L -->(kf) [RU(H2O)(5)L](2+) + H2O was followed as a function of temperature and ethylene concentration (up to 40 MPa) using a homemade high gas pressure NMR microreactor. The reaction was first order in H2C=CH2 with 10(3)kf(298)/kg mol(-1) s(-1) = 1.22 +/- 0.06, Delta H(f)double dagger/kJ mol(-1) = 76.9 +/- 2, and Delta S(f)double dagger/J K-1 mol(-1) = -42.9 +/- 8. These results confirm previous works on mono-complex formation reactions where an Id mechanism was proposed. The reaction [Ru(H2O)5L]2+ + *L reversible arrow(kL) [Ru(H2O)(5)*L](2+) + L of exchange of L on the mono-complex was followed for L = H2C=CH2 (10(3)k(L)/kg mol(-1) s(-1) = 10.8 at 298.2 K), Me2SO (0.35 at 278.5 K), and CO (0.052 at 298.3 K); the rate-determining step is the rupture of the Ru-(HOax)-O-2 bond with trans-Ru(H2O)(4)L-2](2+) as reaction intermediate. Due to the trans effect exercised by these strong pi-accepting ligands, the ligand exchange reaction is faster than the mono-complex formation reactions. The cis-bis-complex formation reaction, [Ru(H2O)(5)L](2+) + L -->(kcis) cis-[Ru(H2O)(4)L-2](2+) + H2O, was also investigated for L = MeCN (10(3)k(cis)/kg mol(-1) s(-1) = 0.111 at 298.1 K), Me2SO (0.019 at 321.6 K), and H2C=CH2 (0.007 at 298.1 K, Delta H(cis)double dagger/kJ mol(-1) = 129.9 +/- 4, and Delta S(cis)double dagger/J K-1 mol(-1) = +92.0 +/- 11); here, too, the Ru-H2Oeq bond breaking is rate determining, but due to the decrease of the lability of water molecules cis to pi-accepting ligands, these reactions are much slower. In the case of MeCN, the reaction scheme includes the formation of the trans-bis-complex and of the mer-triscomplex. As a general rule, the rate of these complex formation reactions,of dissociative nature, can be predicted from the oxygen-17 determined water exchange rates.
引用
收藏
页码:5915 / 5924
页数:10
相关论文
共 41 条
  • [1] MONOCOMPLEX FORMATION REACTIONS OF HEXAAQUARUTHENIUM(II) - A MECHANISTIC STUDY
    AEBISCHER, N
    LAURENCZY, G
    LUDI, A
    MERBACH, AE
    [J]. INORGANIC CHEMISTRY, 1993, 32 (13) : 2810 - 2814
  • [2] Trans- and cis-water reactivities in d6 octahedral ruthenium(II) pentaaqua complexes:: Experimental and density functional theory studies
    Aebischer, N
    Sidorenkova, E
    Ravera, M
    Laurenczy, G
    Osella, D
    Weber, J
    Merbach, AE
    [J]. INORGANIC CHEMISTRY, 1997, 36 (26) : 6009 - 6020
  • [3] PROTON CHEMICAL-SHIFTS OF AQUEOUS ALUMINUM SALT SOLUTIONS
    AKITT, JW
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1973, (11): : 1177 - 1181
  • [4] CIS-DIHALOTETRAKIS(DIMETHYL SULFOXIDE)RUTHENIUM(II) AND TRANS-DIHALOTETRAKIS(DIMETHYL SULFOXIDE)RUTHENIUM(II) COMPLEXES (RUX2(DMSO)4, X = CL, BR) - SYNTHESIS, STRUCTURE, AND ANTITUMOR-ACTIVITY
    ALESSIO, E
    MESTRONI, G
    NARDIN, G
    ATTIA, WM
    CALLIGARIS, M
    SAVA, G
    ZORZET, S
    [J]. INORGANIC CHEMISTRY, 1988, 27 (23) : 4099 - 4106
  • [5] A SIMPLE MULTI-NUCLEAR NMR THERMOMETER
    AMMANN, C
    MEIER, P
    MERBACH, AE
    [J]. JOURNAL OF MAGNETIC RESONANCE, 1982, 46 (02) : 319 - 321
  • [6] PREPARATIVE USES OF HEXAAQUARUTHENIUM(II) - SYNTHESIS OF PHOSPHINE COMPLEXES
    BAILEY, OH
    LUDI, A
    [J]. INORGANIC CHEMISTRY, 1985, 24 (16) : 2582 - 2585
  • [7] BARNES JR, 1979, J CHEM RES-S, P350
  • [8] SYNTHESIS AND PROPERTIES OF SUBSTITUTED RUTHENIUM AQUA COMPLEXES
    BERNHARD, P
    LEHMANN, H
    LUDI, A
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1981, (23) : 1216 - 1217
  • [9] SYNTHESES AND CRYSTAL AND MOLECULAR-STRUCTURES OF HEXAAQUARUTHENIUM(II) P-TOLUENESULFONATE AND HEXAAQUARUTHENIUM(III) P-TOLUENESULFONATE, [RU(H2O)6](C7H7SO3)2 AND [RU(H2O)6](C7H7SO3)3.3H2O
    BERNHARD, P
    BURGI, HB
    HAUSER, J
    LEHMANN, H
    LUDI, A
    [J]. INORGANIC CHEMISTRY, 1982, 21 (11) : 3936 - 3941
  • [10] A MODIFIED SYNTHESIS OF RUTHENIUM(II) HEXAAQUA SALTS
    BERNHARD, P
    BINER, M
    LUDI, A
    [J]. POLYHEDRON, 1990, 9 (08) : 1095 - 1097