J. inorg, nucl. Chem., 1973,Vol. 35, pp. 3763-3767. PergamonPress. Printedin Great Britain.

T H E C A R B O N Y L A T I O N O F RuC13 . x H 2 0 I N
REFLUXING ETHANOL

MARK L. BERCH and A. DAVISON

Department of Chemistry, Massachusetts Institute of Technology,
Cambridge, Massachusetts 02139

(Received 12 January 1973)

Abstract--The well ~cnown red solution prepared by the passage of CO through a refluxing solution of
RuCI a .xHzO in ethanol is shown to contain Ru(CO)2C12, fac-[Ru(CO)3C13]- and Ru(CO)C13/
[Ru(CO)CIs] -2. Ambiguities in the preparation and spectra of these and other ruthenium carbonyl
halides are discussed.

INTRODUCTION
IF CO is passed through a refluxing solution of RuCI3. xHzO in ethanol, a bright
red solution is obtained. Solutions prepared similarly in 2-methoxyethanol are
yellow[i, 2]. Since its discovery in 1964 by Chatt[1], a wide variety of Ru(II) and
Ru(III) complexes have been prepared from this red solution without any report of
its composition. We wish to point out that one batch of commercially available
ruthenium trichloride hydrate gave different results when subjected to carbonylation
in ethanol. We have confirmed the original preparation of the red solution with a
variety of samples of ruthenium trichloride hydrate from a number of sources, e.g.
Alfa Inorganics, Engelhard Industries and Mathey Bishop, Inc. A careful reexamin-
ation of the original preparations[I] together with our anomalous results sheds much
light on the nature of the red solutions. We describe the identification of the carbonyls
present in these solutions and comment on some of the discrepancies which have
been reported for various Ru(II) carbonyl halide systems.

THE NORMAL REACTION TO PRODUCE A RED SOLUTION

When CO is passed through a refluxing solution of RuC13 . x H 2 0 in absolute
ethanol, careful monitoring of the reaction by i.r. spectroscopy, in the carbonyl
region, shows quite clearly that the composition of the solution is markedly de-
pendent upon the reaction time. Almost immediately a peak is seen at c a . 2041 cm- 1.
By 40 min, two additional weak peaks appear at 2069 and 1998 cm- 1. The solution
at this point is usually dear red. As the reaction continues the intensity of the
2041 cm- 1 absorption decreases and there is a concomitant growth in the intensity
of the other two peaks. Later a weak peak, often obscured by a weak solvent
absorption, appears at 2131 cm- 1. By 42 hr the 2041 cm- 1 peak is no more than a
I. J. Chatt, B. L. Shaw and A. E. Field, J. chem. Soc. 3466 (1964).
2. J. L. Dawes and J. D. Holmes, Inorg. nucl. Chem. Lett. 7, 847 (1971).

3763
3764 MARK L. BERCH and A. DAVISON
shoulder on the 2069 cm-1 peak and shortly thereafter becomes no longer dis-
cernible, although the solution remains red. After 2-4 days, the solution lightens to
orange and then quickly becomes clear yellow. After the disappearance of the
2041 c m - i peak there is no further change in the i.r. spectrum.
In the previous work this yellow solution was not achieved because the reaction
was stopped after 4-5 hr.

THE ANOMALOUS REACTION "'

We have consistently observed a different reaction course from one batch of
RuC13. xH20, Alfa Inorganics lot "July 7, 1969". The reaction mixture, which was
initially reddish-orange prior to the passage of CO, at reflux turned briefly green.
Then a small amount of finely suspended solid was produced to give an opaque
greenish-blue mixture. After 4.5-8.5 hr the solution clarified to become bright
yellow. A small amount of grey solid was deposited, which was not found in the
yellow solutions obtained from the normal reaction. We have monitored a number
of reactions using samples of RuC13. x H 2 0 from this lot. The results are somewhat
variable. The yellow solutions contain sharp peaks at 2131 and 1998 cm-1 with a
broader band at 2069-2059 cm-1. In those solutions in which the intensity of the
2131 cm- 1 absorption is very weak the central band is near 2069 cm- 1, relatively
sharp, and about the same intensity as the 1998 c m - 1 peak (cf. the normal reaction).
If the 2131 cm -1 peak is intense, the central band is nearer 2059 cm -1, relatively
broad, and more intense than the 1998 cm-1 peak. If the carbon monoxide and heat
are shut off immediately after the solution turns yellow, exposure to air will cause it
to turn orange or orange-red within a few hours. This change can be reversed by
refluxing with the passage of CO. If the reaction continues several hours after the
time it becomes yellow, the resulting solution, (I), will turn orange only after several
weeks of exposure to air and will remain unchanged in a stoppered flask for over a
year. Evaporation of the yellow solution (I) gave a mobile yellow oil which was
extracted with CH2C12. The addition of heptane to this extract caused the separation
of a dense yellow powder (II). This material is no longer soluble in CH2CI 2. Any
residue from the CH2C12 extraction can be dissolved in boiling ethanol and the.
process repeated to yield more (II). The yellow solution (I) gives Ru(CO)2C1/(PPhah,
as does the conventional red solution[3] when it is reacted with triphenylphosphine.
This batch of ruthenium trichloride hydrate gave yellow solutions with i.r. spectra
similar to (I) when the reaction was run in 2-methoxy ethanol, n-butanol, methanol
and t-butanol. We have identified three species present in the red and yellow solutions.
These are discussed below.
Ru(CO)2C12
If(II) is washed briefly with CH2C12 and dried in v a c u o (150 °, 4 x 10 -3 mm Hg) for
60 hr the yellow powder obtained has an i.r. spectrum consistent with Ru(CO)2C12.
A n a l . Calcd. for C2C1202Ru: C, 10-54; C1, 31.10; Ru, 44.33. Found: C, 10.65; C1,
30.99, Ru, 44-34. Previous workers have noted[4, 5] that when acid solutions con-

3. T. A. Stevensonand G. Wilkinson,J. inorg, nucl. Chem. 28, 945 (1966).

4. J. Halpern, B. R. James and A. L. W. Kemp,J. Am. chem. Soc. 88, 5142 (1966).
5. R. Colton and R. H. Farthing,Aust. J. Chem. 24, 903 (1971).
 Carbonylation of RuCI 3 . x H 2 0 3765

taining the [Ru(CO)2C14] - 2 ions were evaporated, Ru(CO)2C12 was obtained. When
Ru(CO)2C12 is dissolved in absolute ethanol the i.r. spectrum shows two equally
intense absorptions at 2068 and 1997 cm-1, essentially the same values as seen in
(I). Acidification of this solution with an excess of aqueous HCI causes the bands to
shift to lower frequencies (see Table) which corresponds to
Ru(CO)2C12 -+- 2C1- = [Ru(CO)2C14] -2. (1)
Further, because of the very high yield of the isolated Ru(CO)2C12 in these reactions
there is not likely to be sufficient halide for the equilibrium (1) to be very far to the
right. Thus, we feel that Ru(CO)2C12 (or a solvated form) is the major species present
in both the red and yellow solutions.
There is some confusion in the literature about the solubility of Ru(CO)2CI2.
Though reported as highly insoluble[6, 7] its i.r. spectrum has been reported in
CHC13E6, 83. We find that Ru(CO)2C12 isolated from (I) or prepared according to
the method of Cleare et al.E9] dissolved in ethanol but not in CHCI3. However, if
the material isolated from (I) is evacuated at room temperature rather than 150° it
is partially soluble in CHCIa or CH2C12. This material has unsatisfactory analysis
(high C, H and O and low for Ru and CI) for R u ( C O ) 2 C 1 2 and presumably contains
bound ethanol.
fac_[Ru(CO)aC13] -
The yellow solution (I) possesses a peak at 2131 cm- t which we assign to fac-
[Ru(CO)3C13]-. The other band, at 2051 c m - t is obscured by Ru(CO)2CI 2. The
yield varies in the preparation of (I) from a very minor to a major component as
judged by the relative intensity of the 2131 cm- ~ peak. An extraction of (II) (pro-
duced from solutions containing sizable amounts of fac-ERu(CO)3Cl3]- ) with
CHECI 2 gives a white solid whose i.r. spectrum is consistent with Ru2(CO)6C14.

Table 1. Infrared frequencies of ruthenium carbonyl species

Compound Frequency Medium

Ru2(CO) 6CI 4 2139s 2065vs *

fac-[Ru(CO)3Cl3]- 2131s 2051vs t
Ru(CO)2C12 2068s 1997s *
[Ru(CO)2CI4] - 2 2059s 1986s "t
Ru(CO)C13 2044 *
[Ru(CO)CI~]- 2 2036 t
(I) 213 l w - s 2069-2059s-vs
1998s

* Absolute ethanol.
I" Slightly wet and acidic ethanol ; anions as solvated H +.
Ethanolic reaction mixture

6. B. F. G. Johnson, R. D. Johnston and J. Lewis, J. chem. Soc. (A), 792 (1969).

7. W. Hieber and P. John, Chem. Ber. 103, 2161 (1970).
8. B. F. G. J o h n s o n , R . D. Johnston, P. L. Josty, J. Lewis and 1. C. Williams, Nature, Lond. 213, 901
(1967).
9. M. J. Cleare and W. P. Griffith, J. chem. Soc. (A), 372 (1969).
3766 MARK L. BERCH and A. DAVISON

Anal. Calcd. for C6C1406Ru2: C, 14.07; C1, 27.70; Ru, 39.48. Found: C, 14.08;
Cl, 27.65 ; Ru, 39-10. Previous workers[9] have obtained Ru2(CO)6C14from evapor-
ation of acidic solutions containing [Ru(CO)3CI3]-. If the Ru2(CO)6C14 is dissolved
in EtOH peaks are seen at 2139 and 2065 cm- 1. If this solution is acidified with
excess aqueous HC1 the bands shift to 2131 and 2051 cm-1 corresponding to
Ru2(CO)6C14 + 2C1- -- 2fac-[Ru(CO)3Cl3]-. (2)
The earlier confusion in the literature concerning the i.r. spectrum of Ru2(CO)6C1,,
has been partially resolved in a recent communication by Benedetti et al.[10]. How-
ever, in that and previous work i.r. studies in halocarbon solvents have reported
absorptions in the 2025-2005 cm- 1 region with intensities reported as medium[8, 11]
or weak[6, 11]. In Nujol mulls previous workers[10, 11] report peaks below 2030 cm- 1
but Colton[5] reports none. In addition, its color has been reported as either yellow
or white. Colton[5] has suggested that spectral differences depend upon the method
of i.r. sample preparation and upon whether the compound has been sublimed or
recrystallized.
We have found that Ru2(CO)6CI 4 whether isolated from (II) or prepared via the
method of Cleare et al.[9] is a pale yellow solid with weak bands below 2025 cm -1
in CHC13. Careful fractional crystallization (addition of heptane to the boiling
CH2C12 solution) of this material eventually gave a white solid as the least soluble
component. This solid has no bands below 2025 cm- 1 either in concentrated halo-
carbon solutions (which are colorless) or in a Nujol mull. Sublimination of this pure
material (120 °, 10 -2 mm Hg) caused no change in its color or i.r. spectrum.
Thus, one of the components of the yellow solution is fac-[Ru(CO)3C13]- and it
occurs in lesser amounts in the red solutions.

Ru(CO)C13/[Ru(CO)C15 ]- 2
There is some ambiguity in the assignment of the 2041 cm- 1 peak found in the
red solutions. A solution of [Ru(CO)C15]-2 prepared from refluxing RuCla. x H 2 0
with formic acid, hydrochloric acid 1:1 v/v fo~' 1 hr[9] was evaporated to an amor-
phous solid. According to Colton[5] this material is Ru(CO)Cla contaminated with
RuCI3. When this solid is dissolved in ethanol a reddish-orange-brown solution is
obtained with a peak at 2045 cm-1. If [Ru(CO)C151-2 is prepared by Halpern's
procedure[4] a similar solution with a band at 2043 cm-1 is obtained. If either of
these ethanolic solutions is refluxed with the passage of CO the peak disappears and
two bands appear at 2071 and 2000 cm- 1. After 2-4 days the solution suddenly goes
orange and then shortly thereafter turns yellow. Thus, these solutions behave in a
similar manner to the red solutions.
Attempted preparations of [Ru(CO)C15]-2 using HCO2H-HCI[9] give variable
results depending upon the source of the ruthenium trichloride. We have obtained
the following results.
(i) No reaction from anhydrous RuC13 obtained from Alfa Inorganics or Research
Organic/Inorganic Chemical Corporation.
10. E. Benedetti, G. Braca, G. Sbrana, F. Salvetti and B. Grassi, J. organomet. Chem. 37, 361 (1972).
11. M. I. Bruce and F. G. A. Stone, J. chem. Soc. (A), 1238 (1967).
 Carbonylation of RuCI 3 . xHzO 3767

(ii) Variable results from RuCI3 obtained from Johnson Mathey Company, e.g.
some samples gave partial conversion to Ru(CO)2C12 plus unreacted RuCI3 which
was recovered. Other samples gave partial conversion to [Ru(CO)C15]-2 plus un-
reacted RuC13 .
(iii) Conversion to ERu(CO)CIs]-2, no insolubles remain for RuC13 . x n 2 0 from
Mathey Bishop Company or Alfa Inorganics.
It is unclear whether the 2041 cm -1 peak in the red solutions represent
"RuCOCI3" or its conjugate [Ru(CO)C15] -2 or something in between. The main
difficulty lies in the scant evidence for the formulation Ru(CO)C! 3. The solution
spectrum contains one peak, and the species reacts with CsC1 to give CSEERu(CO )-
C15][5]. These observations are consistent with other possibilities, e.g. IRu(CO)C14
solvent]- or [Ru(CO)C15] -2. Acidification of Ru(CO)C13 in ethanol with con-
centrated aqueous HC1 produced a change in the position of the i.r. absorption from
2044 to 2036 cm -~. There is some variation in the peak position in preparations of
the red solution. In five preparations it has varied from 2037 to 2043 cm- 1. Also, the
2041 cm-1 peak is usually not completely symmetrical. It is likely that the exact
nature of the Ru(III) carbonyl species depends upon the C1- availability as do the
equilibria (1) and (2) e.g.
Ru(CO)CI 3 + 2C1- = [Ru(CO)C14]- + C1- -- [Ru(CO)CIs]-2 (3)
This is consistent with the preparation[3] of EpyH] [Ru(CO)C14py] by addition of
pyridine to the red solutions with no added halide. Colton claims that the carbonyl-
ation of ruthenium(III) in room temperature methanol gives Ru(CO)CI3[5 ]. This
information is of limited value because of the following: (i) "Ruthenium(III)" is
highly ambiguous. RuCI3, RuC13 . x H 2 0 and RuCI6 3 for example might easily
give different carbonylation products. (ii) He gives no evidence to distinguish
Ru(CO)Cl 3 from [Ru(CO)C15]-2; (iii) Methanol differs from ethanol as a reaction
medium particularly for RuCla. x n 2 0 ~ (iv) As Stephenson e t al. have pointed out[3],
commercially available RuCl 3 . x H 2 0 is not an innocent starting material and is
thought to contain some Ru(IV) and various polynuclear species.
Finally, it appears that the Ru(III) carbonyl species is the source of the dimeric
olefin complexes reported by Robinson e t al.[12] as being obtained from the red
solution. When (I), which contains no Ru(III) carbonyl species, is refluxed with
cyclo-octa-l,5-diene no product was obtained. However, the use of a red solution
ca. 75 min old gave a 38 per cent yield of [Ru(CO)CI2(COD)] 2 . The starting solution
had shown mostly the Ru(IlI) species, with a smaller amount of Ru(CO)2C12.
After removal of the product the final yellow solution was depleted in the Ru(III)
species, but showed the Ru(CO)2C12 undiminished. In the original preparation the
yield of the olefin complex was only 17 per cent. The starting solution was c a . 4 hr
old and presumably has much less of the Ru(III) carbonyl species present in the
reaction mixture.

Acknowledgements--We thank the Petroleum Research Fund of the American Chemical Society for
support of this work.

12. S. D. Robinson and G. Wilkinson, J. chem. Soc. (A), 300 (1966).