4557
at the same position or that one tautomer is present in much higher concentration than the others. Derivatization reactions have been carried out by several authors, 2 , 3,6 using a variety of organic reactants. They found reaction only with the nitrile tautomer. We have carried out reactions of LiCH2CN with MgCI, and HgCI, and of C6HjCH(Li)CN with MgCI,. The infrared spectra of the magnesium compounds show absorptions near 1650 cm-' (C=N) and 3300 cm-l (N-H) with no absorption in the C=N region. The mercury compound on the other hand shows a strong absorption at 2180 cm-' (C=N) and only very weak absorptions at 1632 and 3200 cm-'. Magnesium chloride either preferentially reacts with one of the tautomers or re-
arranges to give a species with a C-N fragment; mercuric chloride, on the other hand, gives only the nitrile form. The lithium derivatives of acetonitrile and phenylacetonitrile represent a unique class of organolithium compounds which d o not have the typical electrondeficient framework. The general bonding scheme for LiCH2CN is one of intermolecular association with the lithium of one molecule interacting with the cyanide of a n adjacent molecule. The lithium derivative of phenylacetonitrile is dimeric with the lithium of one molecule interacting with the cyanide of the other molecule. Studies of other nonelectron-deficient lithium compounds are currently underway.
Oxygen-18 Tracer Studies with the trans-Dioxobis ( ethylenediamine) rhenium ( V ) Ion ([Re(en),O,]+) Louis B. Kriege' and R. Kent Murmann* Contribution from the Chemistry Department, University of Missouri, Columbia, Missouri 65201. Received October 28, 1971 Abstract: The rate of exchange of oxygen atoms between the trans-dioxobis(ethylenediamine)rhenium(V) ion and
solvent water has been determined. The effect of changing the [H+], [ethylenediamine], ionic strength, temperature, supporting electrolyte, solvent, and the presence of other acids and bases on the rate has been investigated. The exchange has been studied over the [H+]concentration range from 4.17 X 10-5 M to 6.03 X iM. At pH 7.00, the concentration of total uncoordinated ethylenediamine present was varied from 0.0 to 0.4397 M . At 50.0" and I.( = 1.50 (KCl), the rate law is given by R/[Re(en)202f]= ko kenh,[enH2*+] f k,,[en] + k,,h[OH-]. Values for k o ,k&,, k,,,, and k& at this temperature were found to be 7.86 f 1.52 X 10-j sec-l, 647 =t 0.37 X M-l sec-', M-' sec-l, and 3.26 + 0.31 X 10-1 M-I sec-l, respectively. The Arrhenius activation energies 1.42 i 0.10 X are 30.4 i.2.7, 30.5 & 0.4, 18.1 f 3.5, and 24.2 f2.0 kcal/mol, respectively. The rate of oxygen exchange was found t o be dependent upon the nature of the positive ion of the supporting electrolyte and appears t o be general acid-base catalyzed. Partial substitution of methanol for water as the solvent increased the rate. When the rrans-[Re(er~)~O?l+ ion is oxidized, a general feature is that the trans O=Re=O group of the rhenium(V) complex is transferred essentially intact to the product Reo4- ion. With C10- ion as the oxidant, 1.908 + 0.043 of the oxygen atoms in Reo,- came from the rhenium(V) complex and 2.158 i 0.024 came from solvent water. With Mn04- as the oxidizing agent, 1.706 i 0.032 oxygen atoms were transferred. When O3 was used to oxidize the complex, 1.953 =t 0.009 oxygen atoms were transferred to Reo4- and 1.620 + 0.006 of the oxygen atoms came from the solvent water.
+
n order to perform oxygen-transfer experiments on the oxidation of [Re(en)?02]+ to Reo4-, it was necessary to know the rate equation for exchange of oxygen atoms between [Re(en),O,]+ and water. The rate law for the oxygen exchange between Reo4- and solvent water has been reported.? This paper reports the rate law for the exchange of oxygen atoms between [Re(en)20y]+and solvent water and its dependence upon solvent composition and temperature. The results of oxygen- 18 transfer experiments are reported for the oxidation of [Re(en)202]+to Reo4- using several oxidizing agents.
I
( I ) Abstmctcti i n part from the Ph.D. thesis of L. B. Kriege, University of ,Missouri, 1971. (2) R. I,O,]+
4562
found to be kenh2 = 6.79 f 0.46 X l e 3 M-' sec-l, ken = 1.42 f 0.10 X M-'sec-l, and koh = 3.26 f 0.31 X 10-l M-' sec-I. The value for kenhzfrom the pH dependence data can be compared to that found from the ethylenediamine dependence data at pH 7.00, which was 6.47 f 0.37 X M-' sec-', in reasonable agreement. Figure 2 shows a graph of log R/[Re(en)202+]VS. p H showing the experimental points and the calculated least-squares line. The experimental data fit the proposed rate law sensibly, considering the restrictive constants ko, Kl, and Kz for en. Table VI1 contains values for R/[Re(en)202+]obsdand R/[Re(en)20z+]ca~cd for each point shown in Figure 2. The Arrhenius activation energy for k, and koh was obtained by conducting two runs at 39.9" and two at 30.0". The ko and kenhrterms were subtracted from the overall rate and solution of the simultaneous equations gave values for ken and koh at these temperatures. Plots of In k us. 1/T gave an E, of 18.1 f 3.5 kcal/mol with log A = 9.4 f 2.4 for kenand 24.2 f 2.0 kcal/mol with log A = 15.8 =t1.4 for koh. Experiments designed to determine if other bases increased the rate of oxygen exchange of [Re(en)z02]+are presented in Table VIII. Values for kestd were calculated from the pH-dependence studies.
Table IX shows that as the methanol to water ratio increases the rate constant of oxygen exchange increases. The results of the tracer studies on the oxidation of [Re(en)20z]C1to ReOl- using enriched complex, normal H20, and normal C 1 0 - are shown in Table XA. The Table X. Tracer Studies on the [Re(en)zOz]+-C1O- Reaction" Sample
Enrichmentb
K O [Re(en)1021+ Reo4Reo4Reo4Reo4-
A 0.003991 0.02182W 0.012346 0.012827 0.012419 0.012405 Av
~~
B 0.003991 0 ,015872c 0 .004067e C!, 010475 0.010426 0.010326 0.010518
c10HIO tRe(enhOIl+ R e 0 4Reo4ReolReoa-
10.18 7.02 9.90 7.44 10.62
Ethylenediamine 2,6-Lutidine 2,6-Lutidine tert-Butylamine tert-Butylamine
Conditions: 0 045 g of [Re(e11)~0~]Cl per sample, 2.5 % NaClO solution at pH 9.9 (A), 11.6 (B), 0". b T h e enrichment of the "normal" carbon dioxide sample used as a standard was arbitrarily set at O.OD4000. Average of 4 determinations. Average of 18 determinations e Average of 10 determinations. Q
[Basel~~t~i 0,1414 0.103 0.103 0.100 0.100
104kObsd, 104kestd, sec-1 b sec-1
1.79 i 0.02 1.06 f 0.01 0,959 f 0.020 0.687 i 0.004 2.10 i 0.05
1.12 0.780 0.960 0.598 1.88
number of oxygens transferred to the perrhenate ion from [Re(en)202]+was calculated by using the formula 4N~e04-=
Conditions: [Re(en)102+] = 0.040 M , en]^^^^^ = 0.0707 M , 1.50 (KCl), 50.0". kobsd = 0.693/ti/, Estimated value for kobsil without additional added base present.
Table IX. Rates of Exchange in CH30H-H20 Mixturesa
a
lO5kOb,d,b sec-l 3.13 3.39 4.12 5.27
i i i i
0.01 0.03 0.02 0.05
Conditions: [Re(en)I02]Cl = 0.040 M , en]^^^^^ = 0.0707 M , 0.118, pH (with no added CHIOH) 8.68, 50.0". kobsd =
p =
0.693/11/,
methanol, high methanol to water ratios could not be used. Also, in these solvents there exists a problem in knowing the pH of the solutions and its meaning. For this reason the studies were carried out using the same amount of ethylenediamine and HCl in each run so that the pH of the solutions would be 8.68 if no methanol were added. At this pH the effects of a change in acidity are minimized since there is little contribution to the exchange rate except by the ko path. Journal of the American Chemical Society
+ (4 - X)NH%O
where N = 46/(44 45) mass ratio measured for the indicated sample and X i s the number of oxygens transferred. The average number of oxygens transferred to Reoa- was 1.908 f 0.043. The oxidation of [Re(en)20z]+to Reo4- with C10was also carried out using normal complex, normal C10-, and enriched H 2 0 . The number of oxygens found in the perrhenate ion that came from the solvent was calculated from the formula
The results in methanol-water mixtures are shown in Table IX. Since the complex is not very soluble in
0.00 10.00 20.00 30.CO
XNIRe(en)tOr]+
+
p =
C H 3 0 H (ml) added per 100-ml total vol
2.171 2.154 2.121 2.185 Av = 2.158 i 0 024
~
~~
Base used
=
1.874 1.981 1.890 1.887 1.908 f 0.043
No. of oxygens in Reo4- from solvent
Table VIII. Effect of Added Basesa pH
No. of oxygens in Reo4- from [Re(en)2O2If
4NRe04-
=
+ 1.908N[~e(en)t021+
XNHPO
(2.092 - X)NcloTable XB shows that the number of oxygens found in the perrhenate ion that came from the solvent was 2.158 f 0.024. The value found is slightly greater than 2.0 apparently due to a small exchange of the ions with the solvent. N o appreciable 0 transfer from C10- to rhenium occurred. The results of the oxidation of enriched [Re(e11)~0~]+ to Reo4- using normal Mn04- and normal H 2 0 are shown in Table XI, The number of oxygens transferred to the perrhenate ion was found to be 1.706 0.032. The manganese product appeared to be Mn02. The number of oxygens transferred to the perrhenate ion when normal ozone is used to oxidize enriched [Re(en)202]+in normal water is shown in Table XIIA. It was found to be 1.953 f 0.009.
94:13 1 June 28, 1972
*
4563 Table XI. Tracer Studies on the [Re(en)tOn]+-Mn04- Reaction"
Sample
H,O [Re(eii)?O# Reo4ReolR e 0 :Reo4-
Enrichmentb
No. of oxygens in R e 0 4- from [Re(en)sOd+
0 . O392lC 0.021828d 0.011422 0.011794 0 011472 0 011530 Av
=
1.676 1.759 1.687 1.700 1.706
+ 0 032
Conditions: 0.045 g of [Re(en)nOp]C1per sample, [KMn04] = 0.1 N,pH.9.4, room temperature. The enrichment of the "normal" carbon dioxide sample used as a standard was arbitrarily set Average of 18 deas 0.004Oc)O. Average of 4 determinations. terminations.
Table XII. Tracer Studies on the [Re(en)202]+-03Reaction" Sample [ Re(en)?O?]+
HZO 0 3
Reo4Reo4Reo,-
Enrichmentb
No. of oxygens in Reo4from [Re(et~)~O~]+
1 ,947 1.965 1.946 1.953 i 0.009
No. of oxygens in Reo4- from H2180
H,'*O [Re(en)?O,]Reo4Reo4Reo,Reo4-
B 0.004012e 0 .034708d 0.004067J 0,016480 0.016401 0.016507 0.016526
Av
=
1.620 1.610 1.624 1.627 1.620 + O.CO6
Conditions: 0.045 g of [Re(en)nOilC1 in 2.00 ml of solution, pH 7.5. 0". b T h e enrichment of the "normal" carbon dioxide sample used as a standard was arbitrarily set as 0.004000. AverAverage of 4 determinations. e Average of 18 determinations. age of 2 determinations. J Average of 10 determinations.
The [Re(en)202]+-03oxidation reaction was also carried out using normal complex, normal ozone, and enriched water. The exchange of oxygen atoms between ozone and water is slowzounder the conditions of this experiment. The results of this study are shown in Table XIIB. The average number of oxygens found in Reo4- that were derived from the solvent was 1.620 i 0.006. The number of oxygens derived from the ozone is then 0.427. The purpose of the stoichiometry experiments was to determine how many ozone molecules were required for each complex ion. This information also indicates if molecular oxygen is one of the reaction products. In the first trial 9.00 ml of a solution, 0.01805 M in [Re(en),O,]CI and 0.0345 M in free ethylenediamine, was allowed to react with 105.1 ml of an oxygen-ozone gas mixture that contained 1.46 X mmol of Oa/ml. It was found that 0.01648 mmol of complex reacted with this amount of ozone, giving a ratio of 1.08 mol of complex/mol of 0,. In a second trial with no excess ethylenediamine it was found that the ratio was 1.03. (20) 0. L. Forchheimer and H. Taube, J . Amer. Chem. SOC.,76, 2099 ( 1954).
Ri[Re(en)~O~l+ = ko
+ kenh2[enHz2+]+
kdenl
A 0.021828c 0 . O03921d 0 . 004012e 0,012637 0.012716 0.012632 AV =
OS
Discussion Aqueous Formula of the [Re(en)202]+Ion. A singlecrystal X-ray diffraction study2 has shown that the [Re(en)z02]+ion has distorted octahedral geometry in the solid state with a linear O=Re=O trans-dioxo grouping. This work shows that samples of '80-enriched [Re(en)zOz]C1can be dissolved in normal water and precipitated as [Re(en)zOz]Iwith less than 1 % exchange. This shows that the [Re(en)202]+ion retains the essentially octahedral configuration in solution which it has in the solid state. The solution structure, based on spectral interpretation by Basu and Basu,17 cannot be correct. Kinetics of [Re(en)z02]+-HzO Exchange. The rate expression which best describes the rate of oxygen exchange of [Re(en)zOz]+at 50.0" and p = 1.50 (KCl) is given by
+ kOdOH-1
While many other rate equations were tried this form gives the best fit while minimizing the complexity of the equation. It has also been found that: (1) ions such as enHz2+, 2,6-lutidineH+, and tert-butylamineH+ increase the rate; (2) bases such as ethylenediamine and tert-butylamine increase the rate of oxygen exchange ; (3) the rate increases with ionic strength and with the size of the cation of the supporting electrolyte at constant ionic strength; and (4) the rate increases when methanol is partially substituted for water or the solvent. The Arrhenius activation energies found for ko, kenh2,ken, and koh were 30.4 f 2.7, 30.5 i 0.4, 18.1 f 3.5, and 24.2 f 2.0 kcal/mol, respectively. The similarity of the activation energies for k, and kenhlsuggests that similar mechanisms may be involved. The high activation energies found for the ko and kenhz terms suggest that rhenium-oxygen bond breaking is more important in the oxygen exchange process than is rhenium-to-oxygen bond formation with the incoming exchanging species. Toppenj has recently determined the rate of oxygen exchange of [Re(CN)10z]3- with solvent water. He found that at 35.0" and p = 1.00 (KC1) that the rate of oxygen exchange is described by
R
=
kl'[Re(CN)q023-][H+]
+
k4[Re(CN)aOz3-][OH-]0.22[CN-]-0." where kl' = klKe, (Keqis the acid association constant for [Re(CN),OZl3-). Values for k, and k, at 35.0" were found to be 3.42 i 0.05 X lezsec-l and 2.15 =k 0.30 X M-' sec-l, respectively. The activation energies for the kl and k4 paths were 23.3 i 0.3 and 20.3 f 0.1 kcal/mol, respectively. It was also found that the rate of oxygen exchange increased with ionic strength. With [Re02(CN)I]3- no path corresponding to the ko path found in this study was seen. This may be rationalized on the basis of the empty, antibonding s orbitals which CN- but not en has. Thus CN- is capable of accommodating some of the electron density placed on (21) T.S.Khodashova, M. A. Poraj-Koshits, G. I~0~]+. The amido group (en)202]+/03 and thus molecular oxygen is produced. in the equatorial plane of the molecules is able to mulWhile the general feature, retention of the -yl oxytiple bond to the rhenium causing a weakening of the gens, is retained, the partial introduction of an ozonetrans-rhenium-oxygen bonds since the rhenium would oxygen into the coordination sphere of rhenium is not now be less able to accommodate the electron density easily explained by a mechanism capable of being from the oxygens. tested. The fraction transferred is highly reproducible, Although the charge type of the ions [ReO2(CN),I3however, which will facilitate future more detailed and [Re(e11)~0~]+ is quite different, the salt effect and mechanistic studies. At present no information is sensitivity to the size of the positive ion of the salt are available concerning the intermediates or activate about the same. This may be a general phenomenon state(s) of this process, A similar situation exists in for trans-dioxo complexes paralleling their basic bethe oxidation of Pu(II1) to Pu02?+by 0,.23In this havior with respect to acids (logs K,) for the first-acid association constants for [Re02(CN)4]3-and [Re(en)*- case the number of oxygens derived from ozone reaches a limiting value of one in 1.0 M H’. 02]+ are 3.26 f 0.02 and 3.71 f 0.15, respectively (25 ”). Acknowledgment. The use of the Calcomp plotting A general feature of the oxidation of [Re(er~)~O~]+ to computer program written by Dr. David L. Toppen is Reo4- is, on the basis of these first results, that the two gratefully acknowledged. (22) F. Basolo and R. G. Pearson, “Mechanisms of Inorganic Reactions,” Wiley, New York, N. Y . , 1967.
Journal ojthe American Chemical Society
(23) S. W. Rabideau and B. J. Masters, J . Phys. Chem., 67, 318 (1963).
1 94:13 June 28, 1972
