Kinetics and Mechanism of the Reductions of Oxalatotetraamminecobalt(III) by Iron(II), Vanadium(H), and Chromium(II)

被引:41
作者
Hwang, Cordelia [1 ]
Haim, Albert [1 ]
机构
[1] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11790 USA
关键词
D O I
10.1021/ic50085a014
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reduction of oxalatotetraamminecobalt(III) by iron(II), vanadium(II), or chromium(11) obeys the rate law -d In [Co(NH3)(4)CO4+] = k (M2+] M2+ where V2+ = Fe2+, V2+, or Cr2+. At [ClO4-] = 1.0 M and 25 degrees, k = (4.12 0.10) X 10(-4), 45.5 1.5, and (2 1) X 10' M-1 sec(-1) for iron, vanadium, and chromium, respectively. For the iron(II) reduction, Delta H +/- = 18.5 0.2 kcal mol(-1), and Delta S* = 12.1 +/- 0.8 eu. For the vanadium(II) reduction, Delta H+ = 12.3 +/- 0.5 kcal mol(-1) and AS* = 9.8 1.6 eu. Various mechanistic details of these and related reactions are discussed.
引用
收藏
页码:500 / 505
页数:6
相关论文
共 29 条
[1]   REACTIVITY OF CO-ORDINATED OXALATE .6. ACID-CATALYSED AQUATION OF TRISOXALATOCOBALTATE(3) ANION [J].
AGGETT, J ;
ODELL, AL .
JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1968, (06) :1415-&
[2]   EQUILIBRIUM AND KINETIC BEHAVIOR OF (NH3)5COC2O4H2 IN AQUEOUS SOLUTION [J].
ANDRADE, C ;
TAUBE, H .
INORGANIC CHEMISTRY, 1966, 5 (07) :1087-&
[3]  
[Anonymous], 1963, 2367 LA
[4]  
[Anonymous], 1960, 2367 LA
[5]  
[Anonymous], 1989, THESIS STATE U NEW Y
[6]   KINETICS OF OXIDATION OF VANADIUM(2) BY IRON(3) AND CHROMIUM(3) COMPLEXES [J].
BAKER, BR ;
ORHANOVI.M ;
SUTIN, N .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (03) :722-+
[7]   REDUCTION OF VARIOUS CIS- AND TRANS-CHLOROBIS-(ETHYLENEDIAMINE) COBALT (3) COMPLEXES BY IRON (2) [J].
BENSON, P ;
HAIM, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1965, 87 (17) :3826-&
[8]   ELECTRON-TRANSFER REACTIONS INVOLVING CHELATING BRIDGING GROUPS [J].
BUTLER, RD ;
TAUBE, H .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1965, 87 (24) :5597-&
[9]   KINETICS OF REDUCTION OF SOME COBALT (3) COMPLEXES BY CHROMIUM )2) VANADIUM )2) + EUROPIUM )2) [J].
CANDLIN, JP ;
HALPERN, J ;
TRIMM, DL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (06) :1019-&
[10]   OXIDATION OF IRON(2) BY COBALT)3) IN PRESENCE OF CHLORIDE IONS [J].
CONOCCHIOLI, TJ ;
NANCOLLAS, GH ;
SUTIN, N .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (07) :1453-&