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Dodecacarbonyltriruthenium.

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by many orders of magnitude by the addition of salts
of alkali metals to the flame, but the soot formation is
unaffected.
However, it is interesting to note that soot containing
very small quantities of finely divided alkali metal salts
burns much more readily than ordinary soot on subsequent introduction of air. This is also true of the
combustion of soot deposits on surfaces [691.
4. Conclusion
This review has been confined to pure hydrocarbon
fuels, since these are the systems that have been most
thoroughly studied. Soot formation in the flames of
fuels containing oxygen, e.g. ethanol, is also largely
due to acetylene and polyacetylenes, and not to compounds such as higher alcohols or aldehydes 1301- The
question of the effect of hetero atoms (nitrogen, sulfur,
halogens, etc) on the mechanism of soot formation 1701
has been deliberately avoided, since the existing
results in this connection are not yet sufficient to allow
any interpretation.
The same is true of the action of foreign additives in
the flame[4,361. The effects of many substances on
soot formation have already been studied. For prac[69] W. Morgeneyer, personal communication, 1967.
[701 D. B. Scully and R . A . Davies, Combust. and Flame 9, 185
(1965); ibid. 10, 165 (1966).
tical reasons, the question of primary interest was
whether the additive promoted or inhibited soot formation or had n o influence. Thus barium salts of
organic acids have recently been used to reduce soot
formation in diesel motors; however, ideas on the
mechanism of this inhibition are still only conjecture [71,731. The intensification of soot formation by
e.g. sulfur trioxide and halogens is also still only incompletely understood.
For lack of information, the question of the process of
soot formation in hydrocarbon-fluorine and hydrocarbon-chlorine flames has also been avoided, as has
the interesting fact that perchlorinated hydrocarbons
burn with fluorine but d o not form soot, provided that
n o hydrogen is supplied to the flame in any form [721.
I am very grateful to Professor Dr. W . Jost for his kind
and continuous support of my work and for the interest
he has shown in i f . Special thanks are due to Professor
Dr. H . Gg. Wagner for many valuable suggestions and
discussions. I thank the Deutsche Forschungsgemeinschaft and the Fraunhofer-Gesellschaft for their
generous support of the investigations on combustion
processes.
[A 635 IE]
Received: August 16, 1967
German version: Angew. Chem. 80,425 (1968)
Translated by Express Translation Service, London
[71] A. Thomas, personal communication, 1965.
[72] R. A. Durie, Proc. Roy. SOC. (London), Ser. A 211, 110
(1952).
[73] E. Bartholome and H . Sachse, Z . Elektrochem. angew. physik. Chem. 53, 326 (1949).
Dodecacarbonyltriruthenium
BY M. I. BRUCE AND F. G .A. STONEI*I
Dedicated to Prof. H . J . Emelkus on the occasion of his 65th birthday
Since the pioneering work of Mond and his coworkers the metal carbonyls and their derivatives have been under active study, and, as in other areas of inorganic chemistry, research
activity has greatly increased in the last twenty years. Whereas hitherto our knowledge
of the carbonyls of the heavier transition metals has been seriously hampered by a lack
of good methods of synthesis, new preparative methods have recently been developed for
Ru3(C0)12, and many new ruthenium carbonyl complexes are being discovered as its
chemistry is explored.
1. Introduction
Dodecacarbonyltriruthenium was discovered in 1910, but
was not characterized as such. Mond et ul.[ll observed the
formation of volatile rose to orange crystals by the action of
[*I Dr. M. I. Bruce and Professor Dr. F. G. A. Stone
Department of Inorganic Chemistry, University of Bristol
Bristol 8 (England)
[11 L. Mond, N . H i m , and M . D . Cowap, Proc. chem. SOC.
(London) 26, 67 (1910); J. chem. SOC.(London) 97, 798 (1910);
Z. anorg. allg. Chem. 68,207 (1910).
Angew. Chem. internat. Edit.
Val. 7 (1968) 1 No. 6
carbon monoxide o n ruthenium metal at 3OO0C and 350 to
450 atmospheres. Subsequently, a chocolate brown nonvolatile amorphous compound, insoluble in benzene but
soluble in water, was claimed as a product of the same reaction and assigned the formula Ru(C0)z [21.
A more thorough investigation 131 of the ruthenium blackcarbon monoxide system showed that Ru(C0)s was formed
[2] L. Mond and A . E. WulZis, J. chem. SOC.(London) 121, 29
(1922).
[3] W. Munchot and W. J. Manchot, 2. anorg. allg. Chem. 226,
385 (1936).
427
at 180°C and 200 atmospheres, as a colorless volatile liquid,
which, in the presence of sunlight o r on warming to 50 "C in
benzene, readily formed the orange crystalline complex
referred to above. The orange compound was incorrectly
assigned the formula Ruz(CO)g, mainly by analogy with
Fe2(CO)g. A dichroic green-red product, insoluble in most
solvents, but giving intensely green solutions with pyridine
was also obtained, and was thought to be Ru(C0)d. The synthesis of a ruthenium carbonyl by the action of carbon monoxide o n ruthenium disulfide at 200 ' C and 200-300 atmospheres in the presence of copper, zinc, or lead was also reported [41. Much of this early work o n ruthenium and other
metal carbonyls was reviewed by Emelpcls and Anderson [51
in a text which helped to stimulate the growth of modern inorganic chemistry by presenting the subject as offering unlimited opportunities for developing new experimental methods of a physicochemical nature, and the exploration, at
that time, of little known fields.
Table 1. Physical properties of Ru,(CO)IZ.
1 154-155
M.P. ( "C)
IR
v(C0) (cm-1): 2059 (s), 2029 (s), 2010 (m); [a], 1191
2061 (s), 2032 (s), 2015 (m);
Ibl, 1101
2066 (s), 2026 (s), 2004 (m); [cl, [ l l I
v(RuC) (cm-1): 544, 575, 589; [c], I l l ]
I
uv
Unit cell constants
0
Bond distances
(A) [8]
'
oc
I
I/
0
oc
0.984,
[el, PI
100 47';
rfi, 171
* 0.003
1.92 i- 0.03
1.15 0.03
+
~~
C1-Ru-CI:
178.2+ 1.2
C1-Ru-CZ:
90.1 f 1.3
U-RU-CZ: 103.3
1.4
C1 = C-Atom above and below the Ru,-plane
Cz = C-Atom in the Ru3-plane
The color of the carbonyl has been discussed[lzI,
and the absorption at 391 nm has been ascribed
to the metal-metal interactions [131. The high resolution mass spectrum shows successive loss of twelve
carbonyl groups to give a stable Ru; cluster, and no
migration of carbonyl groups to form Ru(CO),' ions
(n>4) occurs, as is observed in the spectrum of
Fe3(C0)12 [14,151.
3. Synthesis
In the last few years a series of syntheses ofRu3(C0)12
have been reported which are of increasing simplicity
and efficiency. Reduction of tris(acety1acetonato)ru0
C
'c
O
I
C
0
Fig. 1. The molecular structures of the trimetal dodecacarbonyls of
ruthenium and iron in the crystalline state.
Ru3(C0)12 is soluble in benzene, toluene, chloroform,
and carbon tetrachloride, but is insoluble in methanol
or water. It is stable to air and to light, both as a solid
and in solution. Some physical properties are given in
Table 1.
[4] W . Hieber and H . Fischer, DRP 695 589 (1940); Chem. Abstr.
35, 5657 (1941).
[5] H . 1. Emelkus and J. S. Anderson: Modern Aspects of Inorganic Chemistry. 1st and 3rd Edit. Routledge and Kegan Paul,
London 1938 and 1960.
[6] E . R. Corey and L. F. Dahl, J . Amer. chem. SOC.83, 2203
(1961).
[7] E. R . Corey and L. F. Dahl, Inorg. Chem. I , 521 (1962).
181 E. R. Corey, E. R . deGil, and L. F. Dahl, to be published.
[9] C . H . Wei and L. F. Dahl, J. Amer. chem. SOC.88, 1821
(1966).
428
2.85
1.000,
0
' c o
s
Ru-Ru:
Ru-C:
C-0:
1.000, b/c = 0.9861, p = 100 "46';
*
I/
c
aib = 0.5496, b/b =
~
Bondangles(') [8]
c c
0
Amax (nm): 490 [dl, 391,310 [dl, 275 [dl, 238; [131
E: 390,5350, 1000.10000,24100; 1131
0.546,
2. Physical Properties of Ru~(CO)IZ
The reddish-orange colored crystalline ruthenium
carbonyl was shown to be incorrectly formulated as
Ru2(C0)9 as a result of a n X-ray crystallographic
study [61 on the presumed O S ~ ( C OThe
) ~ . latter proved
to be a trimeric tetracarbonyl [Os(CO)4]3 with a
molecular structure involving a triangle of osmium
atoms and no bridging carbonyl groups [71. The ruthenium analog was shown to be isostructural, and the
formulation was therefore revised to [Ru(C0)4]3 [GI.
A detailed report of the molecular structure of dodecacarbonyltriruthenium has only recently been given 181.
As shown in Figure 1, Ru3(C0)12 has D3h symmetry;
its structure differs from that established for
Fe3(C0)12 191 in that none of the three metal-metal
bonds is supported by bridging carbonyl groups.
(decomp.)
0"
thenium(rr1) with equimolar mixtures of carbon monoxide and hydrogen at 140-160°C and 200-300 atmospheres in methanol affords Ru3(C0)12 in 76%
yieldf161; the method was later modified to give
Ru(C0)5 1171. Treatment of ruthenium stearate in
hydrocarbon solutions with carbon monoxide and
1101 W. Beck and K . Lottes, Chem. Ber. 94, 2578 (1961).
I l l ] H. P . Fritz and E. F. Paulus, Z. Naturforsch. 186,435 (1963).
2. o b E Chim. 20,1737 (1950).
[13] E. W. Abel and R. A . N . MacLean, unpublished.
[14]R . B. King, J. Amer. chem. SOC.88, 2075 (1966).
1151 J. Lewis, A . R . Manning, J . R . Miller, and J. M . Wilson,
J. chem. SOC.(London) A 1966, 1663.
[I61 G. Braca, G. Sbrana, and P. Pino, Chim. e Ind. (Milano) 46,
206 (1964); DRP 1216276 (1966); Chem. Abstr. 65, 8409 (1966).
[17] F. Calderazzo and F. L'Eplattenier, Inorg. Chem. 6, 1220
(1967).
[12] D . A . Pospekhov,
Angew. Chem. internat. Edit. / Vol. 7 (1968) 1 No. 6
[Ru(C0)212], was first obtained by Munchot and Manhydrogen at 200 “C and 240 atmospheres
leads to
chot
r3J. The dimeric carbonyl halide [ R u ( C 0 ) 3 B r ~ h [ ~ ~ ~ I
the formation of Ru(CO)5, which on decomposition
a molecular structure which is based on octahas
affords Ru~(C0)12in 60% yield.
hedral
coordination for the ruthenium atoms with
The simplest and most efficient preparation of the
two
octahedra
sharing a common edge formed by
carbonyl is by low-pressure (< 10 atm) carbonylation
bridging
halogen
atoms. Isomers are possible, and
of methanol solutions of ruthenium trichloride at
both
white
and
yellow
forms of [Ru(CO)3C1~12are
about 65°C in the presence of zinc as a halogen acknown
1191.
The
trimeric
complexes [Ru(CO)qX213
ceptor 1191; the Ru3(C0)12 obtained is essentially pure,
probably have molecular structures in which the Ru3
large orange crystals forming on the surface of the
cluster is retained.
zinc. Yields are around 70 %, and can exceed 80 % if
the solutions are recycled. In the absence of zinc, the
Reactions of Ru3(C0)12 with thiols also give
dimeric metal carbonyl chloride, [Ru(CO)3C12]2 is
several products, viz., [Ru(C0)3SR]2, polymeric
formed in high yield, along with a small amount of
[Ru(CO)2(SR)21n (R = CH3, C2H5, n-C4H9, or C ~ H S ) ,
andRu(SCsHs)3 [26].The iron complex[Fe(C0)3SC2H~lz
a suspension of this carbonyl
R u ~ ( C O ) I ~Stirring
.
chloride in aqueous potassium carbonate solution also
is known to have a structure with bridging SCzH5
gives Ru3(C0)12, in a slow reaction which must ingroups, and in which the S and Fe atoms adopt a
volve disproportionation of [Ru(C0)3C12]2 to give
“butterfly”-like arrangement, as a consequence of
metal-metal bonding [281. The ruthenium analogs
Ru3(C0)12 and perhaps K2[Ru(C0)2C14] [201.
probably have similar structures. The polymeric
Passage of carbon monoxide at ambient pressures into
alcoholic solutions of RuC13 does not afford Ru~(CO)IZ, derivatives [Ru(C0)2(SR)2ln are thought [263 to have
a chain structure similar to that proposed for
but addition of donor ligands yields carbonyl chloride
complexes, e.g. [ C ~ H ~ ( C ~ H ~ ) ~ P ] ~ R U C
orI ~cis( C O ) [Ru(C0)2X2], [291.
[ ( C ~ H ~ ) ~ P ] ~ R U C[211.
~ ~ ( In
C Othis
) ~ way, complexes
Several studies have been made of the reaction becontaining amines 122,231, phosphines [21,221, artween triphenylphosphine and R u J ( C O ) ~ ~
Trinuclear
.
sines 121,221, stibines 1221, a variety of sulfur-containing
compIexes R u ~ ( C O ) ~ [ P ( C ~ H
are~ obtained
) ~ ] ~ L26, 30-321
ligands 123,241, and SnCl3 [22-241 groups as ligands to
btlt different accounts report different carbonyl stretchruthenium have been prepared, as well as some
ing frequencies in the infrared spectra of the products.
diene 1251 complexes.
The metal atom cluster is preserved, but apparently
mixtures of different isomers are formed, the composition of which depends on the solvent employed for the
4. Chemical Reactions of Ru3(C0)12
reaction 1321. Similar reactions with Fe3(CO)12 give
only the mononuclear complexes Fe(C0)4P(C6H5)3
and Fe(C0)3[P(C6H5)3]2 [331, except under the mildest
Following the ready availability of Ru3(C0)12 many
conditions,
when a complex Fe3(CO)llP(C6H5)3 can
aspects of its chemistry and that of its derivatives have
be isolated in 2 % yield [341. Interestingly, crystals of
been explored. A summary of results is given in this
this complex contain a 1:1 mixture of two isomers 1351.
section, with some comparison with analogous reacProlonged refluxing of chloroform solutions of tritions of Fe3(C0)12 where appropriate.
phenylphosphine and Ru3(C0)12 gives an orangeChlorine, bromine, or iodine react with Ru3(C0)12
yellow complex, R U ( C O ) ~ [ P ( C ~ H S ) ~ ]which
C ~ ~ , also
affording four types of complex: mononuclear
appears to be a mixture of isomers [321.
Ru(C0)4X2; binuclear [Ru(C0)3X2]2; trinuclear
[Ru(C0)4X&; and polymeric [Ru(C0)2X2], [26J. Iron
appears to form only the mononuclear and the polymeric species, although the complex Fe(C0)3Br2 1271
may be dimeric and related to [Ru(CO)3C12]2 1261.
[18] M . .4. McGee and G. H. Whitfield, Brit. Pat. 983792 (1965)
I.C.I. Ltd.; Chem. Abstr. 62, 15809 (1965).
1191 M . I. Bruce and F. G. A. Stone, Chem. Commun. 1966,684;
J. chem. SOC.(London) A 1967, 1238.
1201 M . I. Bruce, unpublished.
I271 J. Chatt, B. L . Shaw, and A. E. Field, J. chem. SOC.(London)
1964, 3466.
[22] T . A . Stephenson and G. Wifkinson,J. inorg. nuclear Chem.
28, 945 (1966).
[23] J. V . Kingston, J . W. S . Jamieson, and G. Wilkinson, J. inorg.
nuclear Chem. 29, 133 (1967).
[24] J . V . Kingston and G. Wilkinson, J. inorg. nuclear Chem. 28,
2709 (1966).
[25] S. D . Robinson and G. Wilkinson, J. chem. SOC. (London)
A 1966, 300.
[26] B. F. G. Johnson, R . D . Johnston, P . L . Josty, J . Lewis, and
I. G. Williams, Nature (London) 213, 901 (1967).
I26aI S. Merlin0 and G. Montagnoli, Acta crystallogr. B 24, 424
(1968).
1271 W . Hieber and G . Bader, Z. anorg. allg. Chem. 201, 329
(1931).
Angew. Chem. internat. Edit. / Vol. 7 (1968)
/ No. 6
Reactions between Ru3(C0)12 and tri-n-butylphosphine or triphenyl phosphite also afford trinuclear
complexes Ru3(CO)g(PR3)3, but if the carbonyl is
heated in solution with excess of the phosphine under
CO pressure, mononuclear complexes Ru(C0)3(PR&,
of the type first reported by Collman and RoperC361,
are produced [311. The triphenylarsine complex;
R u ~ ( C O ) ~ O [ A S ( C ~ Hhas
~ ) ~also
] ~ , been made. This
compound reacts more readily than the triphenylphos[28] L . F. Dahl and C. H . Wei, Inorg. Chem. 2, 328 (1963).
1291 F. A. Cotton and B. F. G. Johnson, Inorg. Chem. 3, 1609
(1964).
1301 J . P . Candlin, K . K . Joshi, and D . T . Thompson, Chem. and
Ind. 1966, 1960.
1311 F. Piacenti, M . Bianchi, E. Benedetti, and G . Sbrana, J. inorg. nuclear Chem. 29, 1389 (1967).
1321 M . I . Bruce, C. W . Gibbs, and F. G. A. Stone, unpublished.
[33] A. F. Clifford and A. K . Mukherjee, Inorg. Chem. 2, 151
(1963).
(341 R. J . Angelici and E. E. Siefert, Inorg. Chem. 5,1457 (1966).
135) D . J. Dahm and R. A. Jacobson, Chem. Commun. 1966,496.
[36] J. P. Collman and W . R. Roper, J. Amer. chem. SOC. 87,
4008 (1965).
429
phine complex with carbon tetrachloride or chloroand hydrogen on carbonylated ruthenium trichloride
form [321. Reaction of Ru3(C0)12 with the bidentate
solutions in the presence of silver powder gives
ligand, tetramethyldiphosphine, leads to the forma143,441.
H~RU~(CO
) I ~ Another hydride characterized
tion of [(CH3)2PRu(C0)312[301 which appears to be
by mass spectrometry is H2Ru4(C0)131441. A mixed
similar in nature to [(CH3)2PFe(C0)3]21371. Reaction
hydride HRuC03(C0)12 has been prepared [451, in a
of the ruthenium compound with iodine affords
similar manner to HFeCo3(C0)12 [461, by refluxing
[(CH3)2PRu(CO)3112, presumably by cleavage of the
ruthenium and cobalt carbonyls in acetone, and
ruthenium-ruthenium bond. Reactions between
acidifying the product.
Ru3(C0)12
and
the
tetradentate
ligands
The anion [Ru(CO)4]2- has been used to prepare
[ ~ - ( C ~ H S ~ P C(Qp)
~ H ~and
I ~ [O-(C~HS)~ASC~H~]~AS
P
[ ( C ~ H ~ ) ~ P A U ] ~ R U[decomp.
( C O ) ~ 170 "C; vC0: 2026,
(QAS) have also been studied [381. At 100 "C in chloro1952, and 1935 cm-1 (CSz)] by treatment with
benzene the complexes Ru(C0) (QP) and Ru(C0)
(C~HS)~PA
~C~
1471.
(QAS) are produced; the Ru3 cluster in Ru3(C0)12
There
is
currently
considerable interest in complexes
does not survive reactions with these ligands.
wherein silicon, germanium, or tin atoms are o-bonded
The action of moist nitric oxide in dichloromethane
to transition metals. Recently the chemistry of organoon Ru3(C0)12 affords polymeric [Ru(C0)2(NO)2ln1303.
tin-iron carbonyl compounds has been reviewed, and
Earlier, an unstable red crystalline nitrosyl with the
a number of new complexes described[48]. It was,
unlikely formulation Ru(NO)5 had been claimed as
therefore, of interest to extend this field by studying
the product of treating Ru3(C0)12 with nitric oxide at
ruthenium carbonyl derivatives of the Group 1V
120 "C 131.
elements.
Under appropriate conditions the metal-metal bonds
Treatment of the [Ru(CO)4]2- anion with R3SnCI
in Ru3(C0)12 can be cleaved to give the [Ru(CO)4]2(R = C6H5 or C6H5CH2) affords air-stable fransanion; this is best obtained by the action of sodium in
( R ~ S ~ ) ~ R U (1491.
C O The
) ~ stereochemistry is assigned
liquid ammonia on the carbonyl, evaporation of the
on the basis of the single carbonyl stretching band
ammonia leaving a buff-colored residue, presumably
observed in the infrared spectra of these complexes
NazRu(CO)4 [391. Treatment of this solid with phos(e.g. trans-[(C6H5CH2)~Sn]2Ru(CO)4; m.p. 99 "C,
phoric acid yields H2Ru(C0)4 [401, a hitherto unvC0: 2021 cm-1). In contrast, Me3SnCl and the anion
characterized hydride analogous to the long known
afford cis-[(CH3)3Sn]2Ru(CO)4 (a yellow liquid, b.p.
H2Fe(C0)4. H2Ru(C0)4 is a very unstable colorless
80 "C/10-2 torr, v C 0 : 2084 (s), 2024 (s), 2012 (w), and
liquid which rapidly decomposes to a red-brown solid,
2003 (s) cm-1). With R3SnCl (R = C2H5, n-C3H7, or
probably H ~ R u ~ ( C Oat) temperatures
~~,
above -40 "C.
n-C4H9) mixtures of cis and trans compounds,
In contrast HzOs(CO)4 is stable above 100 "C [411. It is
(R3Sn)2Ru(CO)4, are obtained. Similar complexes are
interesting to speculate that such a polynuclear hydride
formed from Ru(C0)4H2 and trimethyltin hydride or
could have a molecular structure in which the three
triphenyltin chloride [401.
ruthenium atoms form a bent metal-metal sequence
The complexes (R3Sn)zRu(C0)4 are best obtained by
as in HRe2Mn(C0)14 [421. Mononuclear H2Ru(C0)4
reacting triorganotin hydrides with RuJ(CO)I~ It
exhibits a high field proton resonance at T = 17.6 in
had been shown earlier that the iron analogs can be
its NMR spectrum, and a ruthenium-hydrogen stretchprepared similarly from iron carbonyls 1481. However,
ing frequency v(Ru-H) = 1980 cm-1 in its IR specwith the ruthenium carbonyl a novel type of diamagnettrum. In D2Ru(C0)4, v(Ru-D) occurs at 1380 cm-1.
ic complex RloSn4Ru2(C0)6 is also produced, albeit in
H2Ru(C0)4 reacts with phosphines to give the comlow yield. These polynuclear tin-ruthenium compounds
plexes H2Ru(C0)2(PR3)2, which are more convenientare probably formed in the reactions by thermal dely prepared by reduction of the readily available
composition of the mononuclear ruthenium species,
(R~P)2Ru(C0)2C12 (R = C ~ H S or C6H5) with
since pyrolysis of [(CH3)3Sn]2Ru(C0)4produces some
~)~]~;
LiAIH4 [4OJ (e.g. H ~ R U ( C O ) ~ [ P ( C ~ H1H-NMR:
(vC0:
(
C H ~ ) I O S ~ ~ R U (~I () C
O ) ~2036 (w), 2000 (s), and
7 = 18.48, J(P-H) = 24 Hz (triplet)). These hydrides
1982 (m) cm-I), which has the novel molecular strucundergo the expected reactions, such as with chlorinatture shown, as established by an X-ray crystallographic
ed solvents (CHC13 or cc14) to give (R3P)zRu(CO)zCh,
study [SO].
and with Me3SiC1 or Me3SnC1 to give the corresponding ( R ~ P ) ~ R U ( C O ) ~ [ M ( C (M
H ~=
) ~Si
] ~or Sn) com1431 J. W . S. Jamieson, J. V. Kingston, and G. Wilkinson, Chem.
Commun. 1966, 569.
plexes.
Several polynuclear ruthenium carbonyl hydrides have
been characterized. The action of carbon monoxide
[44] B. F. G . Johnson, R . D . Johnston, J . Lewis, and B. H . Robinson, Chem. Commun. 1966, 851.
[45] M . J. Mays and R . N . F. Simpson, Chem. Commun. 1967,
1024.
[37] R . G. Hayter, Inorg. Chem. 3, 711 (1964).
[38] M . T . Halfpenny and L. M. Venanzi, private communication.
1391 J. D. Cotton, unpublished.
1401 M . I . Bruce, J. D. Cotton, and F. G. A. Stone, J. chem. Soc.
(London) A 1968, in press.
[41] F. L'Eplattenier and F. Calderazzo, Inorg. Chem. 6, 2092
(1967).
[42] M . R . Churchill and R. Bau, Inorg. Chem. 6, 2086 (1967).
430
[46] P. Chini, L. Colli, and M . Peraldo, Gazz. chim. ital. 90,1005
(1960).
[47] C. T . Sears, unpublished.
1481 J . D. Cotton, S . A. R . Knox, I. Paul, and F. G . A. Stone,
J. chem. SOC.(London) A 1967, 382.
[49] J. D. Cotton, S . A. R . Knox, and F. C . A. Stone, Chem.
Commun. 1967, 965.
1501 S. Watkins and P. Woodward, unpublished.
Angew. Chem. internat. Edit.
Vol. 7 (1968) / No. 6
proposed, being very similar to those of complexes of
type [R3PMn(C0)4]2. The high resolution mass spectrum of (2), besides showing a molecular ion has a
strong peak corresponding to (CH3)3SiRu(CO);.
Reactions between Ru3(C0)12 and triorganosilanes follow a different course, complexes such as
(2) (m.p. 129 'C; sublimes at 50 "QlO-3 torr) being
produced in high yield. In contrast, under comparable conditions trimethylsilane and Fe3(C0)12 do not
afford a stable silicon-iron complex. Moreover, with
trichlorosilane Ru3(C0)12 gives [Cl3SiRu(C0)4]2
(3) [511, whereas Fe3(CO)12 yields cis-(C13Si)2Fe(CO)4
Dimeric
complexes
and
[C12SiFe(CO)& 1521.
[R2SnFe(CO)& analogous to [C12SiFe(C0)4]2 are
well known but iron complexes similar to ( I ) and (2)
or (3) have not been prepared. Reaction of (2)
with trimethylstannane gives [(CH3)3Sn]zRu(C0)4 and
(CH3)3SiH, but apparently the presence of the chlorine
atoms in ( 3 ) enhances the stability of the siliconruthenium and ruthenium-ruthenium bonds since (3)
does not react with trimethylstannane.
me SnH
Ru3(C0)1z
y
meloSn4Ruz(CO)6 + ( ~ n e ~ S n ) z R u ( C O ) ~
t
Complex (2) undergoes a novel reaction with triphenylphosphine affording [ ( C ~ H S ) ~ P ] ~ R U ( and
CO)~
[(CH~)~S~]~RU(CO)~[P(C~H~)~]~;
under comparable
conditions (3) does not react with the phosphine.
Reactions between Ru3(C0)12 and several hydrocarbons have been investigated. Unlike in the corresponding reactions involving Fe3(C0)12, several of the
ruthenium complexes retain the metal atom cluster,
for example, one product from cycloocta-l,3-diene is
formulated as C ~ H & U ~ ( C O ) I[30]
O and another from
diphenylacet ylene as [ ( C ~ H S ) ~ C ~ ] ~ R ULs31.
~(CO)~
Diphenylacetylene affords several complexes, depending on the reaction conditions. I n one
studyL541, in which the products were separated
by thin-layer chromatography, complexes of formula ( C ~ H ~ ) Z C Z R U ~ ( [C( ~
C)~~H, S ) Z C Z ~ Z R U ~ ( C ~ ) ~ ,
( C ~ H S ) Z C ~ R U Z ( C[ ~
(C
) ~~, H S ) Z C Z ~ ~ R U ~ ( C ~ ) ~ ,
[ ( C ~ ~ S > Z ~ Z ~and
Z ~ ~
[ (Z
C~
( H
~ ~~ ) )~ ~C ,Z ] Z R ~ ( C ~ ) ~
were obtained. The formulas of several of these complexes are similar to those of compounds obtained
from acetylene and Fe3(C0)121551. Structures may
in some cases be assigned by analogy, thus
[(C6Hs)2C2]2R~2(C0)6formed from the carbonyl and
diphenylacetylene in decalin at ZOO "C is probably
(4) [531.
me3SiRu(CO),Ru(CO)4Sime,
me&H
Na/Hg in T H F
m e = CH,
Scheme 1.
Organosilicon and organotin complexes from Ru,(CO),~.
The discovery that an anion [(CH3)3SiRu(C0)4]- can be
obtained from (2) has led to the synthesis of a complex (CH3)3Sn[(CH3)3SiJRu(C0)4 in which two different group I V elements are bonded to ruthenium. Formation of [(CH3)3SiRu(C0)4]- from (2) is reminiscent
of the well known formationof [(C6H5)3PMn(CO)4]from [ ( C ~ H S ) ~ P M ~ ( C O )The
& infrared spectrum of
(2) in the carbonyl region (vC0: 2040 (w), 2015 (vs),
and 2010 (w, sh) cm-1) is in accord with the structure
{Sl] S . A. R. Knox and F. G. A. Stone, unpublished.
[SZ] W. Jetz and W. A . G. Graham, J. Amer. chem. SOC.89,2773
(1967).
Angew. Chem. infernat. Edit.
VoI. 7 (1968) No. 6
The products obtained from similar reactions
with other acetylenes depend on the substituents
present [531. 4,4'-Dichlorodiphenylacetylene
gives
dark red
[ ( c ~ c ~ H ~ ) ~ ~ ~ ] ~ analogous
R u ~ ( ~ O ) ~ ,
to [ ( C ~ H S ) Z C ~ ] ~ R U mentioned
~ ( C ~ ) ~ above, and
orange [(C1C6H4)2C2]2RU3(C0)8 which probably has
a structure similar to that of the black isomer of
1.531 C. T . Sears and F. C . A . Stone, J. organometallic Chem. 11,
644 (1968).
[54] G. Cetini, 0. Cambino, E . Sappa, and M . Valle, Atti Accdd.
Sci. Torino, I, CI. Sci. fisiche, mat. natur 101, 813 (1967).
I551 E. H . Braye and W . Hiibel, J. organometallic Chem. 3 , 38
(1965); and references cited therein.
43 1
[ ( C ~ H ~ ) Z C ~ I ~ FL561.
~ ~ ( 3-Hexyne
C O ) ~ f531 and hexafluoro-2-butyne[571 afford tetra-substituted cyclopentadienone-ruthenium
tricarbonyl
complexes,
(R4C4CO)Ru(C0)3 (R = C2H5 or CF3) as the major
products, along with trace amounts of what are probably polynuclear complexes. Dimethyl acetylenedicarboxylate is quantitatively trimerized to C6(C02CH3)6
on heating with RuJ(CO)IZ1531.
1,3-Cyclohexadienes react with R U ~ ( C Oto
) ~give
~ the
corresponding tricarbonylcyclohexadieneruthenium
compounds 1261. The product from 2,5-dihydroanisole
is a single isomer (5), in contrast to the mixture of isomers formed from iron carbonyl. Proton abstraction
with trityl tetrafluoroborate gives the cation (6).
Tetracyclone and Ru3(C0)12 yield tricarbonyltetracycloneruthenium [571. A ligand-exchange reaction
occurs with tetraphenylcyclobutadienepalladium(1r)
bromide to give 7r-(C6H5)4C4Ru(C0)31531. Tricarbonylcyclobutadieneruthenium has been prepared [581 by
treating 3,4-dichlorocyclobutene with the anion
[Ru(C0)4]2-.
By refluxing cyclooctatetraene and Ru3(C0)12 in a
hydrocarbon solvent at least four complexes are obtained. The compound ?t-CgH8Ru(CO)3[59,601 is the
analog of X - C ~ H ~ F ~ ( C
O )a~ complex which has
[61],
been studied extensively on account of its being a
stereochemically non-rigid molecule [62-651. The ruthenium complex also exhibits a temperature-dependent 1H-NMR spectrum but one capable of greater
resolution at low temperatures. These studies [59,601
have established that the molecular structure of the
ruthenium compound, and almost certainly that of
the iron complex, in solution involves 1,3-diene to
metal bonding 163,651 rather than 1,5-coordination of
the CgH8 ring [641.
The compound CsHsRu(C0)3 undergoes 1,2-addition
reactions 1661 with suitably active molecules such as
1561 R . P. Dodge and V. Sehomaker, J. organometaliic Chem. 3,
274 (1965).
[57] M . I. Bruce and J. R. Knight, J. organometallic Chem. 12,
411 (1968).
[58] R. G. Amief, P. C. Reeves, and R. Pettit, Chem. Commun.
1967, 1208.
[59] M . I . Bruce, M . Cooke, M . Green, and F. G. A . Srone,
Chem. Commun. 1967,523.
[60] W . K . Bratton, F. A . Cotton, A. Davison, A . Musco, and J.
W . Faller, Proc. nat. Acad. Sci. USA 58, 1324 (1967).
1611 T. A . Manuel and F. G. A. Stone, J. Amer. chem. SOC. 82,
366 (1960).
[62] B.Dickensand W.N.Lipscomb,J.chem.Physics37,2084(1962).
[63] F. A. L. Anet, H . D. Kaesz, A. Maasbol, and S. Winstein,
J. Amer. chem. SOC. 89, 2489 (1967); F. A. L. Anet, J. Amer.
chem. SOC. 89, 2491 (1967).
1641 F. A . Cotton, A . Davison, and J . W. Faller, J. Amer. chem.
SOC. 88, 4507 (1966).
[65] C . E. Keller, B. A . Shoulders, and R. Pettit, J. Amer. chem.
SOC.88, 4760 (1966).
1661 M . Green and D . C . Wood, Chem. Commun. 1967, 1062.
432
hexafluoroacetone or (CF3)2C=C(CN)2 to give products such as (7). These reactions are probably similar
to the supposed Diels-Alder adduct of the corresponding iron complex and tetracyanoethylene 167,681.
Cyclooctatetraene is displaced from CgHsRu(C0)3
by iodine or phosphines to give the complexes
[Ru(C0)&]2
and fruns-(R3P)2Ru(C0)3, respectively. Mercuric halides or thiocyanate react with
CgHsRu(C0)3 to afford the binuclear complexes
[Ru(C0)3(HgX)X]2 (X = C1, Br, or SCN), which
further react with pyridine to give the complexes
Ru(C0)3py(HgX)X, which retain the Ru-Hg bond (691.
Other cyclooctatetraene-ruthenium complexes characterized so far include x-C8HgRuz(CO)6 [69,701, icCgH*Ru2(C0)5 [69,7OJ, and (x-CgH&Ru3(C0)4 [701.
The last named complex is particularly novel since it
is both a metal atom cluster compound and a stereochemically non-rigid molecule. The molecular structure (8) has been established for this compound by an
X-ray crystallographic study [711.
Prolonged heating of R u ~ ( C O ) in
I ~ benzene or cyclohexane at 1SO "C gives a new cluster carbonyl formulated as Rug(C0)18 1721. Refluxing the carbonyl in toluene,
xylene, or mesitylene gives other clusters such as red
RUg(C0)17C and purple Rus(C0)14C(arene) [73]. The
hydrocarbons in these reactions may not be the source
of the unique carbon atom but rather a CO group may
have been degraded.
Ultraviolet irradiation of mixtures of R u ~ ( C O ) and
I~
O S ~ ( C Ohas
) ~ led
~ to redistribution reactions affording
Ru20s(C0)12 and RuOsz(C0)12 1741.
Summary
A comparison of the chemistry of Fe3(C0)12 and
Ru3(C0)12 indicates that in the former compound, the
metal-metal bonds are easily broken, and it is only
under the mildest conditions that compounds retaining the Fe3 cluster are obtained. In contrast, the ruthenium cluster is much more robust, and many
structurally new types of complexes with rutheniumruthenium bonds can be obtained, as is evident from
the above review. For this reason further studies on
R u ~ ( C O ) and
I ~ on the osmium analog are likely to be
very worthwhile.
Received: February 1, 1968
[A 641 1EI
German version: Angew. Chem. 80,460 (1968)
[67] A. Davison, W . McFarlane, L . Pratt, and G. Wilkinson,
J. chem. S O C . (London) 1962,4821.
1681 M . D. Rausch and G . N . Schrauzer, Chem. and Ind. 1959,
957.
[69] M . I . Bruce, M . Cooke, and M . Green, J. organometallic
Chem. 13, in press.
[70] F. A. Cotton, A. Davison, and A. Musco, J. Amer. chem. SOC.
89, 6796 (1967).
1711 M . J. Bennett, F. A. Cotton, and P . Legzdins, J. Amer. chem.
SOC.89, 6797 (1967).
[72] F. Piacenti, M . Bianchi, and E. Benedetti, Chem. Commun.
1967, 775.
1731 B. F. G. Johnson, R . D . Johnston, and J. Lewis, Chem. Commun. 1966, 851.
[74] B. F. G. Johnson, J . Lewis, and 1. G. Williams, private communication.
Angew. Chem. internat. Edit. / Yo!. 7 (1968) 1 No. 6
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