You are on page 1of 5

1596

CANADlAN JOURNAL OF CHEMISTRY. VOL. 50, 1972

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 187.144.32.14 on 11/29/12 For personal use only.

A S f . In the neat liquids the results sre more difficult to rationalize unless a larger mutual dipole-dipole interaction leads to a decrease in entropy in transition state 11. The large negative of activation obtained f o r t h e cyclehexane solution of M ~ , N C ( S ) O Mby =emire ~ is not in agreement with this and explanation. However, we feel that the agreement between both laboratories in the results in polar media is the overriding consideration. The lower energy barriers obtained for these mates in many amides 3, is felt to be due to a slight decrease in C-N bond order caused by the inductive effect of the electronegative OCH, group. In conclusion, we can say that considerable caution must be used in evaluating data On hindered rotations in amides since in view of our conclusions the possibility of having a negative AS* for the process is not unreal. It is unfortunate that the precision the (or AS*) determination is so low in the n.m.r.

method otherwise it would be possible to obtain detailed information on the exact nature of the transition state from a variable solvent study.
The authors wish to thank Dr. K. N. Shaw of the University of Waterloo, Waterloo, Ontario, for helpful discussion. Financial support was provided by a Biomedical Sciences Support Grant to Clark University by N.1.H. I. W. H. SIDDALL, and T. H. STEWART. Chem. Rev. 70, 111 517 (1g70). 2. A. ALLERHAND, S. GUTOWSKY, JONAS, H. J. and R. A. MEINZER.J. Am. Chem. Soc. 44, 3185 (1966). 3. P. T . INGLEFIELD, KRAKOWER, W. REEVES, R. E. L. and STEWART. MOI.P ~ Y iS , 6 5 (1968). 5 4. T. DRAKENBERG S. FORSEN. J. Phys. Chem. 74, 1 and (1970). and S. FORSEN. 5. T. DRAKENBERC, V. DAHLQUIST, K. Chem. Stand, 24, 694 (1970), 6. s . BENSON. The foundations of chemical kinetics. McGraw-Hill. 1960. p. 264. 7. A. E. LEMIRE J. C . THOMPSON.Can. J. Chem. 48, and 824 (1970). 8, A, L. VAN GEET. Anal. Chem. 40, 2227 (1968), 9. K . N. SHAWand L. W. REEVES. Chem. Phys. Lett. 10, 89 (1971).

entropy

Zeise's Salt, K[Pt(C,H,)Cl,], Anhydrous and Monohydrate and the Platinum-Olefin Interaction
J. HUBERT, C. KONG, D. ROCHON, T. THEOPHANIDES P. F. AND
Depurtmenr of'C11et~~istry. Universit)~ f Monrreul, Monrrerrl, Quebec o

Received December 14, 1971 Zeise's salt, anhydrous and monohydrate, has been prepared by a new method similar to the original method used by Zeise. The infrared and laser Raman spectra of the anhydrous Zeise's salt together with the infrared spectra of the deutero and bromo analogs, are reported and discussed. The vibrational spectra are interpreted in terms of a cyclopropane-like ring structure, obtained by the insertion of the platinum atom into the double bond.
-

Le sel de Zeise, K[Pt(L)X,] (L = C2H,, X = CI), a ete prepare par une nouvelle methode. Les spectres infrarouges et Raman laser d u sel de Zeise anhydre a I'etat solide sont discutes. Les spectres infrarouges des analogues, pour lesquels L = C2D,, X = CI et L = C2H,, X = Br, sont egalement rapportes. Les absorptions dues B I'interaction platine-double liaison ont ete interpretes en fonction d'un modele cyclique de type cyclopropane, (CH,),PtX,.
Canadian Journal of Chemistry, 50, 1596 (1972)

Introduction The platinum-ethylene bonding in Zeise's salt and the metal insertion into the double bond exhibits unusual features.

There have been conflicting reports concerning the platinum-olefin vibrations in the i.r. spectrum of Zeise's salt (1, 2) and similar platinum-olefin complexes (3, 4). The i.r. spec-

NOT'ES

1597

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 187.144.32.14 on 11/29/12 For personal use only.

Discussion The i.r. and laser Raman spectra of the anhydrous Zeise's salt, the i.r. spectra of the deutero and the bromo analogs are reported in Table 1 . Survey i.r. spectra of the anhydrous salts, K[Pt (C2H4)CI,], K[Pt (C2D4)C1,], and K[Pt(C2H4)Br3]and the hydrated salt K[Pt(C2H4)C13].HI0 are shown in Figs. 1 and 2. Laser Raman spectra are shown in Fig. 3. The spectrum of the monohydrate salt is identical to that reported by Nakamoto and Grogan (1 ). From the spectra, it is evident that the band at 490 cm-' cannot be assigned to water of crystallization, since the band is present in the spectra of the hydrated salt, in the anhydrous salt and also in the bromo analog. It cannot be assigned to a combination band, since both complexes K[Pt(C,H, )Cl,] and [Pt (C2H4)C1,I2 show an absorption band around 490 cm-' and their far i.r. spectra are very different from each Results other. Similarly, this band is observed in the Prei~rwcition of'Zeise'.s Srilt hjl ci Noit. Methocl )Cl, spectra of the complexes [(Pt(C2H4 ),en], The slow reduction of ethanol by an acetylenic [(Pt(CID4)C12 ),en], [(Pt(C2H4 )BrI ),en], and of glycol (ac = (C4Hg)(C2H5)(OH)C-C=C-C- [(Pt(C,H4)C1Br),enI (6). (OH)(C2H5)(C4Hg) or (CH,),C-C-C-CBoth bands at 490 and 400 cm-' are due to (C2H,),) gave as main product Zeise's salt Pt-C stretchings. The assignment was carried (yield: 50-60"/:,). The acetylenic glycol is used as out according to Hiraishi (2b). The bands at a reducing agent to transform ethanol into 400 cm-' (v5) and at 490 cm - ( v l 2 ) are respecethylene in situ. Potassium tetrachloroplatinate tively assigned to the symmetric and the anti-

trum of Zeise's salt has been investigated by many investigators (1-5). The platinum-olefin vibrations have been assigned in Zeise's monohydrate salt, but the presence of water of crystallization in the molecule obscured the 500 cm-' region and resulted in a controversy over the Pt-olefin band assignments (2, 5). The early work of Babuskin et 01. (5c), which was the first attempt to interpret all the bands of the molecule, showed that the ethylene double bond, on complexation, becomes single and that the Pt-C bond strengthwas quite similar to a normal covalent bond. The recent vibrational studies of Hiraishi (2b), as well as the earlier work of Pradilla-Sorzano and Fackler (2ci), are in agreement with the conclusions of the Russian workers. Powell and Sheppard (5b) studied the n.m.r. spectra of a number of olefin complexes including Zeise's salt and came to the conclusion that the C-C bond is a weakly perturbed double bond and that the olefinic molecule is firmly bound to the platinum. This conclusion seems to be contradictory. Earlier, Chatt and Duncanson (lo), from a few features of the i.r. spectra of Zeise's salt, namely, a weak absorption in the region 15001525 cm-', concluded that this very weak band was due to the C=C double bond absorption lowered on complexatio~~ 100- 140 cm- I . by This interpretation implies a weakly perturbed double bond. However, the molecular model they proposed, based on Dewar's model of a- and n-bonding, indicates a strong interaction of the metal with the double bond in agreement with the high shbility of their complexes. This also is a contradictory conclusion. Zeise's salt, anhydrous and monohydrate. has been prepared by a new method similar to the original method used by Zeise.

(11) reacts with ethanol in the presence of the acetylenic glycol as follows:

The complex is recrystallized from acetoneether or water-HC1 solutions. In the above reaction, the water seems to attack the triple bond and hydration with polymerization of the acetylenic glycol takes place. The acetylenic ligand could not be recovered after the reaction and a brown oil was always formed. The presence of the acetylenic glycol and of ethanol are essential for the preparation, since it was impossible to isolate the Zeise's salt without one of them. The reaction is similar to the method used by Zeise to prepare K[Pt(C2H4)C13].H20

'

1598

CANADIAN JOURNAL O F CHEMISTRY. VOL. 50, 1972

TABLE Observed frequencies for the Zeise's salt and its analogs* 1. K[PtC13(C2H4)I Assignment (ref. 8b) K[PtCI,(C2H4)].H20 (sofid)
~

Infrared (solid)

Raman (solid)

K[PtC13(C2D4)I infrared (solid)

K[PtBr3(C2H,)I infrared (solid)

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 187.144.32.14 on 11/29/12 For personal use only.

'The intensities of the Raman lines are relalive to the strongest line (100). w = weak, m = medium, s b = broad.

= strong,

sh

= shoulder,

FIG.I. Survey spectra of (I), K[Pt(C2H4)C13].H20; (II), K[Pt(C2H4)C13]; (III), K[Pt(C2H4)Br3]; (IV), K[Pt(C2D4 )cl31.

symmetric Pt-C stretching vibrations. These bands are shifted on deuteration to 384 and 450 cm-' and are found at 393 and 484 cm-' for the bromo analog. The Raman band at 1253 cm-' is assigned to C-C (v,) stretching (26) from polarization data and the band at 299 cm-' has been assigned to the Pt-C1 (trans) symmetric stretching. The 212 cm-' band can be tentatively assigned to the PtC, rocking (26) and the in-plane 180 cm-' band to the C1-Pt-C1 deformation (36). The recent X-ray study on the Zeise's salt monohydrate showed that the two types of platinum-chlorine bond (i.e. cis and trans) lengths are within one e.s.d. Therefore the difference in length cannot unambiguously be attributed to the truns-influence, since the surroundings of the chlorine atoms are different (7). An older neutron diffraction study (9) indicates that the four hydrogen atoms of the ethylene lie in a plane. The two carbon atoms are 0.18 A above this plane toward the platinum atom. Thus the hydrogen atoms bend back significantly (9) and this should be consistent

NOTES

1599

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 187.144.32.14 on 11/29/12 For personal use only.

FIG.2 . Infrared spectra of Zeise's salt anhydrate (-); its deutero analog (...), the bromo analog monohydrate (-. ), and the bromo analog anhydrate (---), in the region 600-200 cm-' in Nujol mulls and between CsI plates.

with a strongly perturbed C-C bond. However, the authors (9) reported a C-C length of 1.354 (15) A compared to 1.37 (3) A obtained by X-ray diffraction (7). These distances are fairly short, but the uncertainties on the bond lengths are relatively great and the values should be interpreted with great care. The two platinum-carbon bond distances are not significantly different (2.121 (19) and 2.134 (19) A)., These values are not too far from ~ , a platinum-carbon a-type bond (2.076) (15) A (8). A ring structure with two Pt-Ca-type bonds and one C-C single bond with some double bond character as in the case of cyclopropane or ethylene oxide is considered for (CH,),Pt to interpret the vibrational spectra (2a, 5c). This model can be obtained by insertion of the platinum atom into the double bond of the olefin :
PtC1; PtCl;

FIG.3. Laser anhydrate.

Raman

spectra of the Zeise's

salt

PtC1; has an electron affinity comparable to that of the group X in the series of molecules X(CH,),, where X = CH,, 0, S, HN, i . ~ . the , molecules cyclopropane, ethylene oxide, ethylene sulfide, and ethylene amide. The angle cxc is decreasing as the atom X increases in size, cyclopropane (67'), ethylene oxide (60), ethylene sulfide (48-), and Zeise's salt (39 ) seems to fall well in the trend.

Experimental
The i.r. spectra between 4000 and 200 cm-I were obtained with a Perkin-Elmer 621 i.r. spectrophotorneter. Nujol or C4CI, mulls and KBr or Csl techniques were employed to record the spectra. Calibration of the frequencies was made with a polystyrene film and water vapor. Raman spectra were obtained with a Jarell Ash Raman spectrophotometer using He-Ne laser excitation at 6328 A. The samples were examined as crystalline powders. K[Pt(C2H4)C13].H20 was prepared according to the method described by Chatt and Duncanson (10). The anhydrous salt K[Pt(C2H4)CI3]was obtained by recrystallization

+
/

>c=<

n
-c-C

'\

PtCl; seems to be similar in its chemical properties to CH~' in cyclopropane, indicating that

1600

CANADIAN JOURNAL OF CHEMISTRY. VOL.

50. 1972

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 187.144.32.14 on 11/29/12 For personal use only.

i n 4 N hydrochloric acid. The water and HCl were evaporated in a desiccator under reduced pressure. The salt was also prepared by the following method: potassium tetrachlorobla;inite (01002 M ) was dissolved in 15 ml of water and the solution was filtered. A solution of 10 ml of 5.8-diethyl-6,6-dodecyne-5,s diol or 2,2-dimethyl5,s-diethyl-3-heptyne (0.005 M ) in ethanol was added to the above solution. The mixture was stirred for a few minutes and left for a week. It was then filtered and the filtrate evaporated to dryness. The residue was washed with anhydrous ether and dissolved in 20 ml acetone. This was filtered and evaporated to dryness. Finally Zeise's salt was recrystallized slowly in a refrigerator in a mixture of acetoneanhydrous ether. Yield, 60%. K[Pt(C,D,)CI,] was prepared using ethylene-if, gas in D,O and following the method described in ref. 10. K[Pt(C,H,)Br,].H,O was prepared by the above method (10) usinga water solution of K,PtBr,. The red colored complex is extracted with acetone and recrystallized from acetone-ether. The i.r. spectrum of the complex was identical to the reported spectrum (2a). K[Pt(C,H,)Br,] anhydrous was obtained by recrystallization in tetrahydrofuran or in 4 N hydrobromic acid and following the procedure as for K[Pt(C,H,)CI,]. We wish to thank Johnson, Matthey and Mallory Ltd., for the loan of platinum chloroplatinite and the National Research Council of Canada for financial assistance. Many

thanks also to Dr. I. S. Butler, McGill University for the use of the Jarell Ash Raman spectrophotometer.
1. M. J. GROGAN K. NAKAMOTO. Am. Chem. Soc. and J. 88, 5454 (1966). 2. (a) J. PRADILLA-SORZANO J. P. FACKLER, and JR. J. Mol. Spectrosc. 22, 80 (1967). (b) JIROHIRAISHI.Spectrochim. Acta, 25A, 749 (1969). Inorg. Chim. Acta, 3,391 (1970). 3. (u)T. THEOPHANIDES. (b) T. THEOPHANIDES. Unpublished results. and K. NAKAMOTO.Inorg. Chem. 7, 4. G . T. BEHNKE 2030 (1968). and 5. (0) H. B. JONASSEN J. E. FIELD. J. Am. Chem. Soc. 79, 1275 (1957). (b) D. B. POWELL N. SHEPPARD. and Spectrochim. Acta, 13, 69 (1958). (c) A. A. BABUSKIN, L. A. GRIBOV, and A. D. GEL'MAN. RUSS.J. Inorg. Chem. 4,695 (1959). 6. P. C. KONG and T. THEOPHANIDES. Can. Spectrosc. I04 (1969). 7. J. A. J. JAVIS,B. T. KILBOURN, P. G. OWSTON. and Acta Cryst. B27, 366 (1971). 8. R. MASON, B. ROBERTSON, P. 0. WHIMP. J. G. and Chem. Soc. A 535 (1970). 9. W. C. HAMILTON K. KLANDERNAN. and Acta Cryst. A25, S172 (1969). J. 10. J. CHATTand L. A. DUNCANSON. Chem. Soc. 2939 (1953).

Conductivity and Viscosity of the Tetrabutylammonium Bromide - Carbon Tetrachloride System


K. F. DENNING JAMES PLAMBECK AND A.
Department of Chernisiry. University of Alberta, Edmonton, Alberta Received July 20, 1971' Conductivity and viscosity measurements have been made on tetra-n-butylammonium bromide-carbon tetrachloride solutions for the mole ratio range 1 :40 to 1 : 2 at temperatures from 25 to40 "C. At any individual concentration, both conductivity and viscosity follow a n Arrhenius type temperature dependence. Viscosity increases exponentially with tetrabutylammonium bromide concentration while conductivity has a maximum at approximately 1 :5 mole ratio R,NBr-CCI,. Des mesures de conductivite et de viscosite ont e t t effectutes sur des solutions constitutes d'un melange de bromure de tetra-n-butylammonium-tetrachlorure de carbone; les rapports molaires utilises varient de 1 :40 a 1 : 2 pour des temperatures allant de 25 a 40 "C. Pour chaque concentration individuelle, la conductivitt ainsi que la viscositt dependent de la temptrature par une relation du type d'Arrhtnius. La viscositt augmente d'une facon exponentielle avec la concentration en bromure de tetrabutylammonium, alors que la conductivitt passe par un maximum pour un rapport molaire de 1 :5 R,NBr-CC1,.
Canadian Journal of Chemistry, 50, 1600 (1972)

Solutions containing low concentrations of ionic salts, and fused ionic salts, have long been used as electrolytic media, and their conductivities and viscosities are well known. Mixtures
'Revision received February 1, 1972.

which have "solute" and "solvent" present in comparable amounts are less well characterized. Such mixtures can be prepared from tetrabutylammonium halides and carbon tetrachloride (1). We have used such mixtures in