Preparation, chemistry, and structure of new ruthenium complexes

Article abstract of DOI:10.1016/S0022-328X(99)00350-2

Several new monomeric Ru iodide complexes, coordinated to the η⁵-cylopentadienol ligand, were prepared from the dimer complex (η⁵-C₄Ph₄COHOCC₄Ph ₄-η⁵)(μ-H)(CO)₄Ru

Full text of DOI:10.1016/S0022-328X(99)00350-2

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 588 (1999) 92–98
Preparation, chemistry, and structure of new ruthenium complexes
Benjamin Schneider, Israel Goldberg, Dvora Reshef, Zafra Stein, Youval Shvo *
School of Chemistry, Raymond and Be6erly Sackler School of Exact Sciences, Tel A6i6 Uni6ersity, Tel A6i6 69978, Israel
Received 19 April 1999
Dedicated to the memory of Daniel F. Chodosh, a remarkable man, a good friend and an imaginative chemist.
Abstract
Several new monomeric Ru iodide complexes, coordinated to the h5-cylopentadienol ligand, were prepared from the dimer
complex (h5-C4Ph4COHOCC4Ph4-h5)(m-H)(CO)4Ru2, and the monomer complex (h4-C4Ph4CO)(CO)3Ru. Their mode of forma-
tion and chemistry were studied, and their structures were determined by X-ray diffraction analyses. In addition, two structurally
interesting dimeric complexes were unexpectedly formed, and were also structurally characterized. © 1999 Elsevier Science S.A.
All rights reserved.
Keywords: Ruthenium; Iodide; Crystallography; Synthesis; Chemistry
the reactions was conveniently monitored by IR spec-
The organo–ruthenium complex 1 [1a], central to
troscopy and TLC. The reaction products were sepa-
several other related complexes, was found to exhibit
rated by column chromatography, then crystallized and
interesting, diverse, and useful types of catalytic chem-
characterized by X-ray crystallography.
istry, reported by us in several publications [1b–f], as
well as by others [2]. In essence, complex 1 exhibits the
type of chemistry which is associated with its two
fragments 2 and 3, resulting from the thermal dissocia-
Monomeric products 4 and 5 were obtained as out-
lined in Scheme 1. The dimer 6 was formed in a trace
quantity.
The major products 4 and 5 were readily separated
tion of the dimer 1. While 2 (18-electron complex) is
by column chromatography (silica) due to the substan-
stable in solution and could be readily observed by IR
tial difference in their polarity. The physical and spec-
1
and H-NMR, the formation of the unstable 3 (16-elec-
tral properties of the above three complexes are
tron complex) was postulated on the basis of the result-
presented in Table 1. Complexes 4–6 were subjected to
ing catalytic chemistry of 1. The simple synthesis of 1
X-ray diffraction analyses, and their ORTEP diagrams
[1a], its stability, and its simple non-stringent handling
are presented in Figs. 1–3.
conditions, make it an attractive and practical catalyst.
In the present work we have studied stoichiometric
reactions of 1 with methyl iodide. In addition to unrav-
eling the resulting new structures (X-ray crystallogra-
phy), the chemistry involved was anticipated to elicit
new concepts for planning catalytic reactions.
Mechanistically 4 and 5 are considered to originate
from 2 and 3. We are proposing a scheme for the
reaction of methyl iodide with 1, involving its dissoci-
ated species 2 and 3 (Scheme 2).
The transformation of 2 to 5 was supported experi-
mentally. A solution of 2 in benzene was prepared by
1. Chemistry
Complex 1 was reacted under nitrogen in benzene,
and also in THF, with methyl iodide. The progress of
* Corresponding author. Fax: +972-3-6409293.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00350-2

B. Schneider et al. / Journal of Organometallic Chemistry 588 (1999) 92–98
93
Scheme 1.
Table 1
Physical and spectral data
No.
4
M.p. (°C)
195–196
185 dec.
IR a (cm−1
2038, 1989
2038, 1989
)
1H-NMR b l (ppm)
MS
3.50 (s, 3H), 6.9–7.5 (m, 20H)
1.25 (br, 1H, OH), 6.9–7.5 (m, 20H)
683 [M+], 627 [M+−2CO], 556
[M+−I]
5
669 [M+], 613 [M+−2CO], 542
[M+−I]
6
7
2059, 2025, 1982 c
2038, 1990
171–172
217 dec.
1.50 (m, 4H), 3.2 (s, 3H), 3.71 (t, 2.5 Hz, 2H),
3.78 (t, 4.95 Hz, 2H), 6.95–7.51 (m, 20H)
3.56 (s, 6H), 6.92–7.71 (m, 40H)
755 [M+], 699 [M+−2CO], 629
[M+−I]
8
1950
1311 [MH+], 1255 [M+−2CO],
1128 [M+−2COꢀI]
a IR spectra were recorded in dichloromethane.
b NMR spectra were recorded in CDCl3/TMS.
c IR spectrum was recorded in KBr.
that 2 may still exist in a small equilibrium concentra-
tion in the hydrogenation reaction mixture, and in view
of the observed fast transformation of 2 to 5, 1-iodobu-
tane was subjected to H2 pressure (500 psi) in the
presence of a catalytic amount of 5 in benzene at
125°C. The change of substrate concentration was fol-
lowed by GC (internal standard). No reduction took
place in the absence of carbonate. Very slow reduction
did take place in the presence of carbonate after 24 h
(63% conversion; 34 turnovers).
subjecting complex 1 to hydrogen pressure [1a]. Addi-
tion of MeI to this solution gave 5, in a fast reaction, as
a sole product. Thus 2 is the precursor of 5, and
therefore 3 must be the precursor complex of 4 in the
reaction Scheme 1. Furthermore, reacting 3a with
methyl iodide gave 4 as a sole product, most probably
via 3. These results support the contention that the
chemical behavior of dimer 1 in the above, as well as in
other catalytic reactions is that of its dissociated
monomeric constituents 2 and 3. It is noteworthy that
complex 5 was selectively obtained also by reacting the
dimer 1 in benzene–toluene with iodine (see Section 3).
Mechanistically, 4 is obtained via the oxidative addi-
tion of MeI to the coordinately unsaturated 16-electron
complex 3. Complex 5 may be obtained via oxidative
addition of MeI to the Ru atom of 2, followed by
reductive elimination of CH4. However 2 is already a
coordinately saturated 18-electron complex. The essen-
tial vacation of a coordination site may occur via
h5“h3 rearrangement of the cyclopentadienyl system.
The propensity of 2 to readily hydrogenate a CꢀI
bond may provide the basis for a catalytic cycle, pro-
vided that 5 could be hydrogenated back to 2 in situ. In
two separate experiments, 5 was subjected to hydrogen
pressure, 500 psi at 130°C in benzene, in the absence
and in the presence of potassium carbonate. No trace
of 2 could be detected (IR) in the resulting hydrogena-
tion reaction mixtures. Nevertheless, on the assumption
Fig. 1. Molecular structure, and selected crystallographic data for 4.
,
Bond lengths in A: Ru1ꢀI 2.693(1); Ru1ꢀC2 1.882(5); Ru1ꢀC4
1.899(6); C2ꢀO3 1.127(6); C4ꢀO5 1.116(6); C6ꢀO11 1.329(6); Ring
CꢀC (av.) 1.44490.021.

94
B. Schneider et al. / Journal of Organometallic Chemistry 588 (1999) 92–98
Complex 7 (Fig. 4) was obtained from the reaction of
1 with MeI in THF, rather than benzene. Formally, the
resulting structure implies iodo methylation cleavage of
THF, with the resulting methoxy-4-iodobutane reacting
with 1 to give 7, depicted below. It is not clear whether
the THF ring cleavage is catalyzed to any extent by the
ruthenium complexes present in the reaction solution.
,
Fig. 2. Selected crystallographic data for 5. Bond lengths in A: Ru1ꢀI
2.691(1); Ru1ꢀC2 1.885(6); Ru1ꢀC4 1.878(7); C2ꢀO3 1.145(6); C4ꢀO5
1.122(6); C6ꢀO11 1.346(5); Ring CꢀC (av.) 1.43790.015.
Attempts to exchange a CO ligand with CH3CN by
several hours reflux of 4 in acetonitrile failed. Resorting
to trimethylamine oxide [3] (Shvo reagent) in acetoni-
trile led instead to the instantaneous formation of
dimer 8, the iodine being a better ligand than acetoni-
trile. This complex has a point symmetry, and is stable.
The IR spectrum of 8 exhibits a single CO stretching
band. Its X-ray structure is presented in Fig. 5.
The reluctance of 5 to undergo oxidative addition of
H2 may be attributed to the reduced electron density on
the metal atom due to the Ruꢀhalogen bond, or to its
inability to undergo h5“h3 bond rearrangement. The
reduced electron density was evident by the relatively
high IR stretching frequencies of the CO groups bound
to the metal (vide supra).
In conclusion, complexes 4 and 5 can now be ob-
tained selectively with good yields in separate reactions.
Thus, complex
4
can be generated from (h4-
C4Ph4CO)(CO)3Ru (3a) with methyl iodide, while 5 is
obtained by the action of iodine on (h5-
C4Ph4COHOCC4Ph4-h5)(m-H)(CO)4Ru2 (1). It stands
to reason that other O-alkylated complexes, isostruc-
tural with 4, can be prepared in a similar manner.
These may serve as synthons for cationic Ru complexes
after iodine abstraction, and may possibly function as
polymerization and metathesis catalysts. The thermal
dissociation of 8 is of interest, since it will generate a
reactive Ru(d6)ꢀ16-electron complex.
Fig. 3. Molecular structure, and selected crystallographic data for 6.
(Asterisked and nonasterisked labels relate to the two parts of this
2. Structures
,
structure across the iodine bridge.) Bond lengths in A: Ru1ꢀI
2.727(1); Ru1*ꢀI 2.714(1); Ru1ꢀC2 1.897(8); Ru1*ꢀC2* 1.891(8);
Ru1ꢀC4 1.889(6); Ru1*ꢀC4* 1.907(6); C2ꢀO3 1.149(10); C2*ꢀO3*
1.143(10); C4ꢀO5 1.133(8); C4*ꢀO5* 1.119(8); C6ꢀO11 1.235(7);
C6*ꢀO11* 1.255(6); C6ꢀC7 1.480(9); C6*ꢀC7* 1.448(7); C7ꢀC8
1.439(7); C7*ꢀC8* 1.451(7); C8ꢀC9 1.449(8); C8*ꢀC9* 1.448(8);
C9ꢀC10 1.443(9); C9*ꢀC10* 1.422(7); C6ꢀC10 1.480(7); C6*ꢀC10*
1.464(8). Ru···Ru* 4.848.
The numbering of important atoms in the five struc-
tures that were analyzed by X-ray diffraction is pre-
sented for convenience in the following scheme, where
R=H, or alkyl group (for 6, R is nonexistent). It
should be noted that Ph groups (omitted) are bound to
positions 7, 8, 9, and 10 of the ring.

B. Schneider et al. / Journal of Organometallic Chemistry 588 (1999) 92–98
95
Scheme 2.
In agreement with a Cp ring being a better s donor
than cyclopentadienone, a shift of the IR CO stretching
bands to higher wave numbers in 6 compared to 4 was
observed (Table 1). The average C6ꢀO11 bond in 6 is
,
0.084 A shorter than in 4, reflecting on a substantial
carbonyl p-bonding. The two ring carbonyls deviate
,
markedly from the C7ꢀC10 plane by 14.0° (0.222(5) A)
,
and 17.0° (0.256(5) A) for Cꢀ6, the direction being
The structural parameters as well as the IR spectra of
complexes 4, 5 and 7 are very similar. In accordance
with a dicarbonyl structure, their IR spectra, which are
identical, exhibit two carbonyl stretching bands. The
rather high frequency (2038 cm−1) implies weakly
bound RuꢀCO groups.
The hapticity of the ring in these complexes is as-
sumed to be five. No clear bond alternation within the
Cp rings could be discerned, and the rings are essen-
tially planar. The average Ru distances to the four ring
away from the Ru atom. The structural data indicate
no bond alternation in the ring 1,3-diene system. This
has also been previously observed with the X-ray struc-
ture of (h4-C4Ph4CO)(CO)3Ru (3a) [1h], and attributed
to back donation from the occupied metal d-orbitals to
the LUMO of the diene. However, the two bonds
,
flanking the carbonyl group (1.480(7) and 1.480(9) A)
are clearly longer than the average distance
,
C7ꢀC8ꢀC9ꢀC10 (1.443 A). Furthermore, the average
Ru distances to the four ring C atoms, C7ꢀC10, in the
,
C atoms C7ꢀC10 in 4 and 5 are 2.231 and 2.248 A,
respectively. The corresponding RuꢀC6 distances are
,
2.359(5) and 2.312(5) A. The RuꢀC6 bond elongation
may be attributed to minor non-planarity of the 5-
membered ring. Dihedral angles of 6.5 and 2.9° are
formed by the plane inscribing C6 and its two flanking
C atoms with the C7ꢀC10 plane in 4 and 5. The
deviation of C6 from the C7ꢀC10 plane in 4 and 5 is
,
0.093(5) and 0.041(5) A, respectively, and is away from
the Ru atom. Such h5-coordination results in
Ru(II)ꢀ18-electron complexes.
The combined electron counting of the dimer 6 is 35,
with a mean oxidation state of 1/2. The Ru atoms are
equidistant from the bridging iodine atom, with a
RuꢀIꢀRu angle of 126°. The Ru···Ru* distance of 4.848
,
A indicates no bonding between the two metal atoms.
,
The average RuꢀI distance is 0.027 A longer than the
,
Fig. 4. Selected crystallographic data for 7. Bond lengths in A: Ru1ꢀI
covalently bound I atom in 4 (i.e. by 27s), thus ac-
counting for its bridging of the neighboring Ru atom.
2.698(1); Ru1ꢀC2 1.847(13); Ru1ꢀC4 1.873(16); C2ꢀO3 1.125(14);
C4ꢀO5 1.149(16); C6ꢀO11 1.341(12); Ring CꢀC (av.) 1.44490.020.

96
B. Schneider et al. / Journal of Organometallic Chemistry 588 (1999) 92–98
Several doubly iodine bridged Ru dimer complexes
are recorded in the literature, but none with Cp ligands
[5]. However, only two such complexes with the iodine
atoms as the only bridging atoms (RuꢀRu bond), were
,
reported. The RuꢀI bond lengths of 2.766, 2.761 A are
somewhat longer than those measured for 8.
3. Experimental
3.1. (p5-2,3,4,5-Tetraphenyl-1-methoxycyclopentadi-
enyl)(iodo)dicarbonyl Ru(II) (4) and (p5-2,3,4,5-tetra-
phenylcyclopentadien-1-ol)(iodo)dicarbonyl Ru(II) (5)
Dimer 1 (500 mg; 0.46 mmol) and methyl iodide (660
mg; 4.6 mmol) were dissolved in benzene (46 ml). The
solution was refluxed for 5 h until the disappearance of
the CO IR stretching band of 1. The solvent was
removed in vacuum, and the residue chromatographed
on silica starting with methylene chloride (15%),
petroleum ether (85%). Complex 4 emerged with
methylene 20:80 chloride–petroleum ether, and com-
plex 5 with methylene chloride. With ethyl acetate as
eluent, a minute quantity of 6 was obtained as red
crystals. The X-ray structures of 4, 5 and 6 are pre-
sented in Figs. 1–3.
Fig. 5. Molecular structure and selected crystallographic data for 8.
,
Bond lengths in A: Ru1ꢀI 2.7271(5); Ru1ꢀI* 2.7338(4); Ru1ꢀC2
1.869(4); C2ꢀO3 1.144(5); C6ꢀO11 1.333(4); Ring CꢀC (av.) 1.4509
0.020.
,
two rings are 2.228 and 2.217 A, while the distances
,
RuꢀC6 are 2.480(5) and 2.473(5) A. These data clearly
support an h4-coordination of the 1,3-diene of the
cyclopentadienone ring. The mode of formation of 6 is
not clear.
3.2. (p5-2,3,4,5-Tetraphenylcyclopentadien-1-ol)(iodo)-
dicarbonyl Ru(II) (5)
To the best of our knowledge (October 1998 version
of the Cambridge Crystallographic Database), no Ru
complex, bridged by a single iodine atom only, has
been reported in the literature. The structural fragment
RuꢀIꢀRu has been established in dimer complexes hav-
3.2.1. Method A
A
solution of h5-(2,3,4,5-tetraphenylcyclopenta-
dienol)hydridocarbonyl Ru(II) (2) in benzene was pre-
pared by hydrogenating 1 (100 mg; 0.09 mmol) in
benzene (15 ml) in a stainless steel glass lined autoclave
at 500 psi of hydrogen at 120°C for 4 h (IR: 2018, 1959
cm−1). The solution was cooled and methyl iodide (0.5
ml; 8 mmol) was added. After 1 h reflux under nitro-
gen, the reaction solution showed IR bands at 2038 and
1989 cm−1, and a single TLC spot identical with that
of 5. Evaporation of the solvent, and MS of the solid
confirmed its molecular weight (Table 1).
,
ing, in addition, a RuꢀRu bond (2.759–2.794 A) and
bridging chelating ligands [4].
As with complexes 4, 5, and 7, no clear bond alterna-
tion within the Cp ring could be discerned in 8. h5-Co-
ordination is supported by the essentially planar Cp
ring, and hence 8 is a Ru(II)ꢀ18 e complex.
The two RuꢀI bond lengths in 8 differ by only 0.007
,
A, which amounts to 0.4%, and are therefore, essen-
tially equivalent. However, the average RuꢀI bond
3.2.2. Method B
,
length is 0.037 A (\35s) longer than the covalent
Iodine (234 mg; 0.9 mmol) was added to a solution of
1 (100 mg; 0.09 mmol) in dry benzene (10 ml), and the
mixture kept under nitrogen at room temperature (r.t.)
for 2 h. The resulting solution was washed with a
saturated sodium thiosulfate solution, then dried over
MgSO4. After solvent removal, the residue was chro-
matographed on silica. The pure product 5, which was
collected with methylene chloride (82 mg; 66%), had an
IR spectrum and TLC identical to the product obtained
by method A above.
RuꢀI bond in 4, consistent with a bridging iodine atom
via pp–dp interaction. The RuꢀCO bond in 8 is 0.021
,
A (4s) shorter relative to the average RuꢀCO bond
distance in 4. This substantial shortening also induced a
significant shift of the CO IR stretching band to lower
frequency (1950cm−1; Table 1). Taken together, iodine
bridging of the two monomeric units must be strong,
thus also accounting for the stability of 8 in refluxing
acetonitrile.

B. Schneider et al. / Journal of Organometallic Chemistry 588 (1999) 92–98
97
3.3. (p5-2,3,4,5-Tetraphenyl-1-methoxycyclopenta-
dienyl)(iodo)dicarbonyl Ru(II) (4)
those in the disordered fragments or solvates of some of
the structures). The hydrogen atoms were located in
calculated positions to correspond to standard bond
lengths and angles, methyls being treated as rigid
groups.
A solution of h4-(C4Ph4CO)(CO)3Ru (3a) (100 mg;
0.18 mmol) and methyl iodide (250 mg; 1.8 mmol) in
toluene (10 ml) was refluxed under nitrogen for 3 h.
The IR spectrum of the reaction mixture indicated the
disappearance of all starting complex. After evapora-
tion under vacuum, the residue was chromatographed
on silica. With a solvent mixture of dichloromethane
(70%) and petroleum ether (30%) a solid 4 (77 mg; 64%)
was obtained, which had a TLC and IR spectrum
identical to the product obtained in Section 3.1.
3.6.2. Crystal and experimental data
Compound 4: C32H23IO3Ru·CH2Cl2, formula weight
768.4, monoclinic, space group P21/n, T=298 K, a=
,
12.074(1), b=17.791(1), c=14.528(1) A, i=96.76(1)°,
3
V=3099.0 A , Z=4, Dcalc=1.647 g cm−3, F(000)=
,
1512, v(Mo–Ka)=17.1 cm−1, crystal size ca. 0.20×
0.15×0.08 mm, 2qmax=56.6°, 182 detector frames,
7653 unique reflections, R1=0.053 for 3490 observa-
tions with Fo\4|(Fo) and R1=0.125 (wR2=0.150) for
3.4. (p5-2,3,4,5-Tetraphenyl-1-(4-methoxybutoxy)-
cyclopentadienyl)(iodo)dicarbonyl Ru(II) (7)
all unique data, ꢀDzꢀ51.00 e A−3. The CH2Cl2 solvate
,
A glass lined stainless steel autoclave was charged
with 1 (108.4 mg; 0.1 mmol), THF (10 ml) and methyl
iodide (142 mg; 1.0 mmol). The mixture was purged
with nitrogen, and the closed reactor was heated at an
oil bath temp of 140°C for 4 h. The reaction solution
was cooled, the solvent removed in vacuum, and the
residue dissolved in methylene chloride, and chro-
matographed on silica with methylene chloride. The
product 7 was obtained by elution of the column with
Et–Ac. It was crystallized from benzene, followed by
methylene chloride–cyclohexane.
was found to be partially disordered.
Compound 5: C31H21IO3Ru, formula weight 669.5,
monoclinic, space group P21/n, T=298 K, a=
,
12.132(1), b=10.260(1), c=21.278(1) A, i=96.91(1)°,
3
V=2629.3 A , Z=4, Dcalc=1.691 g cm−3, F(000)=
,
1312, v(Mo–Ka)=18.0 cm−1, crystal size ca. 0.20×
0.10×0.07 mm, 2qmax=56.6°, 179 detector frames,
6517 unique reflections, R1=0.041 for 1965 observa-
tions with Fo\4|(Fo) and R1=0.193 (wR2=0.089) for
all unique data, ꢀDzꢀ50.55 e A−3, the hydroxyl proton
,
was located on a difference-Fourier map.
Compound 6: (C31H20O3Ru)2I·H2O, formula weight
3.5. [(p5-2,3,4,5-Tetraphenyl-1-methoxycyclopenta-
dienyl)(carbonyl)]2Ru2(v-I)2 (8)
1228.1, triclinic, space group P1, T=298 K, a=
(
,
13.353(1), b=13.693(1), c=16.585(1) A, h=81.45(1),
3
,
i=78.09(1), k=78.94(1)°, V=2893.2 A , Z=2,
calc=1.410 g cm−3, F(000)=1222, v(Mo–Ka)=11.0
cm−1, crystal size ca. 0.25×0.20×0.15 mm, 2qmax
Trimethylamine oxide (27 mg; 0.36 mmol) was added
to a solution of 4 (482 mg; 0.7 mmol) in acetonitrile (25
ml) under nitrogen. The heterogeneous mixture was
stirred at r.t. for 4 min, after which it became homoge-
neous, acquiring a purple color. The solution was
washed with water (2×10 ml), and the solvent evapo-
rated in vacuum. Dark crystals of 8 were obtained from
the evaporation residue, using methylene chloride–
petroleum ether as crystallization solvent. The X-ray
structure of 8 is presented in Fig. 5.
D
=
56.7°, 348 detector frames, 14 334 unique reflections,
R1=0.054 for 9338 observations with Fo\4|(Fo),
R1=0.094 (wR2=0.186) for all unique data, ꢀDzꢀ5
−3
,
1.01 e A
.
This compound crystallized as a hydrate; the ana-
lyzed crystal appeared to contain also additional sol-
vent species (possibly water or EtOAc), which could
not be identified in the crystallographic refinement. The
contribution of the unrecognizable solvent (occupying
3
,
3.6. Crystal structures analyses
about 490 A — i.e. 17% of the unit cell volume), was
subtracted from the diffraction pattern by the ‘Bypass’
procedure [9]. The H2O molecule was found also to be
partially disordered. In the crystal it bridges between
adjacent molecules of the ruthenium complex by hydro-
gen bonding to one carbonyl site of each species and
creating a chained arrangement.
3.6.1. Crystal structure analyses of compounds 4–8
The X-ray diffraction measurements were carried out
on either a CAD4 (7, ꢀ–2q scan mode) or a Kap-
paCCD (4–6 and 8, 1° ƒ-scans) Nonius diffractometer
equipped with a graphite monochromator, using Mo–
,
Ka (u=0.7107 A) radiation. The intensity data were
Compound 7: C36H31IO4Ru, formula weight 755.6,
monoclinic, space group P21/c, T=298 K, a=
empirically corrected for absorption. The structures
,
were solved by Patterson and direct methods (SHELXS
-
14.702(7), b=20.355(4), c=21.869(3) A, i=93.02(2)°,
3
86 [6] or DIRDIF-96 [7]) and refined by full-matrix
least-squares based on F2) (SHELXL-97) [8]). Non-hy-
drogen atoms were treated anisotropically (except for
V=6535 (3) A , Z=8, Dcalc=1.536 g cm−3, F(000)=
,
3008, v(Mo–Ka)=14.6 cm−1, crystal size ca. 0.40×
0.30×0.20 mm, 2qmax=46°, 8503 unique reflections

98
B. Schneider et al. / Journal of Organometallic Chemistry 588 (1999) 92–98
with positive intensities, R1=0.084 for 6926 observa-
Science Foundation founded by the Israel Academy of
Sciences and Humanities.
tions with Fo\4|(Fo), R1=0.099 (wR2=0.258) for all
−3
,
unique data, ꢀDzꢀ51.66 e A
.
The asymmetric unit in this structure consists of two
molecules of the organometallic complex, one reason-
ably well ordered and the other partly disordered. The
latter involves different orientations of the ꢀ(CO)2I
tripod at different sites in the crystal, a disorder which
could be modeled in part by an interchange between the
positions of the I and one of the CO ligands with
relative occupancies of 64 and 36% of these ligands at
the two sites. Conformation of the aliphatic residue in
both molecules was found to be disordered as well (as
a result of which most atoms here were assigned an
isotropic U), and the two terminal atoms in the second
species could not be located. The two molecules of the
asymmetric unit differ also in the relative orientations
of the aryl groups.
References
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(1986) 7400. (b) Y. Blum, D. Czarkie, Y. Rahamim, Y. Shvo,
Organometallics 4 (1985) 1459. (c) Y. Shvo, D. Czarkie, J.
Organomet. Chem. 315 (1986) C25. (d) Y. Shvo, M. Abed, Y.
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Shvo, D.F. Chodosh, Inorg. Chim. Acta 97 (1985) L25.
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Compound 8: C31H23IO2Ru. CH2Cl2, formula weight
[3] (a) Y. Shvo, E. Hazum, J. Chem. Soc. Chem. Commun. (1974)
336. (b) Y. Shvo, E. Hazum, J. Chem. Soc. Chem. Commun.
(1975) 829.
(
740.4, triclinic, space group P1, T=117 K, a=
,
10.189(1), b=11.991(1), c=12.127(1) A, h=94.16(1),
3
,
i=103.05(1), k=91.71(1)°, V=1437.9 A , Z=2,
calc=1.710 g cm−3, F(000)=728, v(Mo–Ka)=18.3
cm−1, crystal size ca. 0.35×0.25×0.05 mm, 2qmax
[4] (a) J.A.K. Howard, P. Woodward, J. Chem. Soc. Dalton Trans.
(1977) 366. (b) K.J. Edwards, J.S. Field, R.J. Haines, B.D.
Homann, M.W. Stewart, J. Sundermeyer, S.F. Woolla, J. Chem.
Soc. Dalton Trans. (1996) 4171. (c) J.A. Cabeza, C. Landazuri,
L.A. Oro, D. Belletti, A. Tiripicchio, M. Tiripicchio Camellini, J.
Chem. Soc. Dalton Trans. (1989) 1093. (d) H. Jungbluth, H.
Stockli-Evans, G. Suss-Fink, J. Organomet. Chem. 377 (1989)
339. (e) Kom-Bei Shiu, Wei-Ning Guo, Tsung-Jung Chan, Ju-
Chan Wang, Lin-Shu Liou, Shie-Ming Peng, Ming-Chu Cheng,
Organometallics 14 (1995) 1732.
[5] (a) A. Colombie, G. Lavigne, J.-J. Bonnet, J. Chem. Soc. Dalton
Trans. (1986) 899. (b) J.R. Zoeller, Inorg. Chem. 25 (1986) 3933.
(c) N.J. Holmes, A.R.J. Genge, W. Levason, M. Webster, J.
Chem. Soc. Dalton Trans. (1997) 2331. (d) Kom-Bei Shiu, Luh-
Tin Yang, Shih-Wei Jean, Chien-Hsing Li, Ru-Rong Wu, Ju-
Chun Wang, L in-Shu Liou, M.Y. Chiang, Inorg. Chem. 35
(1996) 7845.
D
=
60.0°, 183 detector frames, 7057 unique reflections,
R1=0.042 for 6199 observations with Fo\4|(Fo),
R1=0.048 (wR2=0.145) for all unique data, ꢀDzꢀ5
1.00 e A−3, near the molecular framework of the
,
Ru-complex (higher residual peaks (B3.35 e A−3) and
,
troughs (−2.17 e A−3) were observed near the partly
disordered dichloromethane solvate).
,
The molecular structure represents a dimer, two
iodine ligands being coordinated simultaneously to two
inversion related Ru centers.
[6] (a) G.M. Sheldrick, SHELXS-86, in: G.M. Sheldrick, C. Kruger, R.
Goddard (Eds.), Crystallographic Computing 3, Oxford Univer-
sity Press, London, 1985, pp. 175–189. (b) G.M. Sheldrick, Acta
Crystallogr. Sect. A 46 (1990) 467.
[7] P.T. Beurskens, G. Beurskens, W.P. Bosman, R. de Gelder, S.
Garcia-Granda, R.O. Gould, R. Israel, J.M.M. Smits, DIRDIF-96,
Crystallography Laboratory, University of Nijmegen, The
Netherlands, 1996.
4. Supplementary material
The crystallographic data were deposited in the Cam-
bridge Crystallographic Database, with the following
deposition numbers: CSD-115323–CSD-115327 for
compounds 4–8, respectively.
[8] G.M. Sheldrick, SHELXL-97, Program for the Refinement of Crys-
tal Structures from Diffraction Data, University of Go¨ttingen,
Germany, 1997.
Acknowledgements
[9] P. Van der Sluis, A.L. Spec, Acta Crystallogr. Sect. A 46 (1990)
194.
This research was supported in part by The Israel
.