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.
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页码:5915 / 5924
页数:10
相关论文
共 41 条
[1]   MONOCOMPLEX FORMATION REACTIONS OF HEXAAQUARUTHENIUM(II) - A MECHANISTIC STUDY [J].
AEBISCHER, N ;
LAURENCZY, G ;
LUDI, A ;
MERBACH, AE .
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 [J].
Aebischer, N ;
Sidorenkova, E ;
Ravera, M ;
Laurenczy, G ;
Osella, D ;
Weber, J ;
Merbach, AE .
INORGANIC CHEMISTRY, 1997, 36 (26) :6009-6020
[3]   PROTON CHEMICAL-SHIFTS OF AQUEOUS ALUMINUM SALT SOLUTIONS [J].
AKITT, JW .
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 [J].
ALESSIO, E ;
MESTRONI, G ;
NARDIN, G ;
ATTIA, WM ;
CALLIGARIS, M ;
SAVA, G ;
ZORZET, S .
INORGANIC CHEMISTRY, 1988, 27 (23) :4099-4106
[5]   A SIMPLE MULTI-NUCLEAR NMR THERMOMETER [J].
AMMANN, C ;
MEIER, P ;
MERBACH, AE .
JOURNAL OF MAGNETIC RESONANCE, 1982, 46 (02) :319-321
[6]   PREPARATIVE USES OF HEXAAQUARUTHENIUM(II) - SYNTHESIS OF PHOSPHINE COMPLEXES [J].
BAILEY, OH ;
LUDI, A .
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 [J].
BERNHARD, P ;
LEHMANN, H ;
LUDI, A .
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 [J].
BERNHARD, P ;
BURGI, HB ;
HAUSER, J ;
LEHMANN, H ;
LUDI, A .
INORGANIC CHEMISTRY, 1982, 21 (11) :3936-3941
[10]   A MODIFIED SYNTHESIS OF RUTHENIUM(II) HEXAAQUA SALTS [J].
BERNHARD, P ;
BINER, M ;
LUDI, A .
POLYHEDRON, 1990, 9 (08) :1095-1097