Metallosite Selectivity Studies in Reactions of Tetrahedral MCo3 Carbonyl Clusters (M = Fe, Ru) with Cyclohexylphosphine. Skeletal Rearrangements Leading to Tri- and Pentanuclear Phosphinidene Clusters and Crystal Structures of RuCo4(μ4-PCy)(μ-CO)2(CO)11 and RuCo2(μ3-PCy)(CO)9

Article abstract of DOI:10.1021/om9902840

We have studied the metallosite selectivity of substitution reactions at heterometallic tetranuclear clusters of the type HMCo₃(CO)₁₂ (M = Fe, Ru). Monosubstitution with PCyH₂ occurs with a different metalloselectivity as a function of M. When M = Fe, substitution of a Co-bound CO ligand occurs whereas when M = Ru, the phosphine ligand is bound to Ru. Introduction of a second substituent (PCyH₂ or NMe₃) occurs in both cases at cobalt and, in the case of HFeCo₃(CO)₁₁(PCyH₂), at a cobalt that does not carry the PCyH₂ substituent. The clusters HMCo₃(CO)₁₁(PCyH₂) (2a, M = Fe; 2b, M = Ru) transform in solution to give the corresponding μ₃-phosphinidene-capped heterotrinuclear clusters MCo₂(μ₃-PCy)(CO)₉ (4a, M = Fe; 4b, M = Ru). The μ₄-phosphinidene-capped intermediate RuCo₄(μ₄-PCy)(μ-CO)₂-(CO)₁₁ (5b) could be fully characterized, whereas the analogous species could not be isolated when M = Fe. The transformation of 2a,b was accelerated by addition of Me₃NO. This work demonstrates that a reaction which represents a partial cluster fragmentation, with a nuclearity change from 4 to 3, may occur via the intermediacy of a larger cluster, of nuclearity 5. Reactions and products were studied by IR and ¹H, ³¹P{¹H}, and ⁵⁹Co NMR spectroscopic methods, and the clusters 4b and 5b have been characterized by X-ray diffraction.

Full text of DOI:10.1021/om9902840

4
908
Organometallics 1999, 18, 4908-4915
Meta llosite Selectivity Stu d ies in Rea ction s of
Tetr a h ed r a l MCo Ca r bon yl Clu ster s (M ) F e, Ru ) w ith
3
Cycloh exylp h osp h in e. Sk eleta l Rea r r a n gem en ts Lea d in g
to Tr i- a n d P en ta n u clea r P h osp h in id en e Clu ster s a n d
Cr ysta l Str u ctu r es of Ru Co (µ -P Cy)(µ-CO) (CO) a n d
4
4
2
11
†
Ru Co (µ -P Cy)(CO)
2
3
9
Soraya Bouherour, Pierre Braunstein,* and J acky Ros e´ *
Laboratoire de Chimie de Coordination, UMR 7513 CNRS, Universit e´ Louis Pasteur,
4
rue Blaise Pascal, 67070 Strasbourg C e´ dex, France
Lo ¨ı c Toupet
Groupe Mati e` res Condens e´ et Mat e´ riaux, UMR 6626 CNRS, Universit e´ de Rennes I,
Avenue du G e´ n e´ ral Leclerc, 35042 Rennes C e´ dex, France
Received April 21, 1999
We have studied the metallosite selectivity of substitution reactions at heterometallic
tetranuclear clusters of the type HMCo
occurs with a different metalloselectivity as a function of M. When M ) Fe, substitution of
a Co-bound CO ligand occurs whereas when M ) Ru, the phosphine ligand is bound to Ru.
3
(CO)12 (M ) Fe, Ru). Monosubstitution with PCyH
2
Introduction of a second substituent (PCyH
the case of HFeCo (CO)11(PCyH ), at a cobalt that does not carry the PCyH
The clusters HMCo (CO)11(PCyH ) (2a , M ) Fe; 2b, M ) Ru) transform in solution to give
the corresponding µ -phosphinidene-capped heterotrinuclear clusters MCo (µ -PCy)(CO) (4a ,
M ) Fe; 4b, M ) Ru). The µ -phosphinidene-capped intermediate RuCo (µ -PCy)(µ-CO)
CO)11 (5b) could be fully characterized, whereas the analogous species could not be isolated
when M ) Fe. The transformation of 2a ,b was accelerated by addition of Me NO. This work
2
or NMe
3
) occurs in both cases at cobalt and, in
3
2
2
substituent.
3
2
3
2
3
9
4
4
4
2
-
(
3
demonstrates that a reaction which represents a partial cluster fragmentation, with a
nuclearity change from 4 to 3, may occur via the intermediacy of a larger cluster, of nuclearity
1
31
1
59
5
. Reactions and products were studied by IR and H, P{ H}, and Co NMR spectroscopic
methods, and the clusters 4b and 5b have been characterized by X-ray diffraction.
In tr od u ction
Phosphines are among the most ubiquitous ligands
portunities for studying the synthesis and reactivity of
isomers which differ by the nature of the metal to which
a given ligand is bound. As a result, investigations
concerning the metallosite selectivity of mixed-metal
clusters have become of increasing importance and we
in transition-metal chemistry and are known to signifi-
cantly alter the structure and/or reactivity of their metal
complexes, in both stoichiometric and catalytic reac-
tions. This has been examined in considerable detail in
mononuclear chemistry and to a large extent with
homonuclear metal clusters. Mixed-metal clusters have
been increasingly used in catalysis, and there is evi-
dence that cooperative effects may lead to improved
2
have recently reported on such aspects. The tetrahedral
carbonyl clusters HMCo3(CO)12 (M ) Fe, 1a ; M ) Ru,
1
b) have proven particularly suitable for such studies,
31
1
59
as they are amenable to P{ H} and Co NMR inves-
tigations. In addition, these clusters have received
3
much attention as catalyst precursors in CO/H2 and
1
properties compared to homometallic systems. Fur-
1
methanol homologation chemistry. They have been
thermore, heterometallic clusters provide unique op-
studied in heterogeneous and homogeneous media, and
in the latter case, phosphine ligands have been shown
to enhance their activity/selectivity. However, the exact
nature of the phosphine-substituted clusters present
†
Dedicated to our friend and colleague Professor Daniel Grandjean
(
University Rennes I), on the occasion of his retirement, with our best
wishes.
*
To whom correspondence should be addressed. E-mail: braunst@
chimie.u-strasbg.fr.
(2) (a) Braunstein, P.; Ros e´ , J .; Granger, P.; Raya, J .; Bouaoud, S.-
E.; Grandjean, D. Organometallics 1991, 10, 3686. (b) Braunstein, P.;
Mourey, L.; Ros e´ , J .; Granger, P.; Richert, T.; Balegroune, F.; Grand-
jean, D. Organometallics 1992, 11, 2628. (c) Braunstein, P.; Ros e´ , J .;
Toussaint, D.; J a¨ a¨ skel a¨ inen, S.; Ahlgren, M.; Pakkanen, T. A.; Pursi-
ainen, J .; Toupet, L.; Grandjean, D. Organometallics 1994, 13, 2472.
(3) (a) Granger, P.; Elbayed, K.; Raya, J .; Kempgens, P.; Ros e´ , J . J .
Magn. Reson. 1995, 117, 179. (b) Richert, T.; Elbayed, K.; Raya, J .;
Granger, P.; Braunstein, P.; Ros e´ , J . Magn. Reson. Chem. 1996, 34,
689.
(1) (a) Braunstein, P.; Ros e´ , J . In Catalysis by Di- and Polynuclear
Metal Cluster Complexes: Heterometallic Clusters for Heterogeneous
Catalysis; Adams, R. D., Cotton, F. A., Eds.; Wiley-VCH: New York,
1
998; p 443. (b) Braunstein, P.; Ros e´ , J . In Comprehensive Organo-
metallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.;
Pergamon Press: Oxford, 1995; Vol. 10, pp 351-385. (c) Braunstein,
P.; Ros e´ , J . In Metal Clusters in Chemistry; Braunstein, P., Raithby,
P. R., Oro, L. A., Eds.; Wiley-VCH: Weinheim, Germany, 1999; Vol.
2
, pp 616-677.
1
0.1021/om9902840 CCC: $18.00 © 1999 American Chemical Society
Publication on Web 11/04/1999

Metallosite Selectivity Studies
Sch em e 1
Organometallics, Vol. 18, No. 24, 1999 4909
polynuclear compounds via P-H oxidative addition.
Although such reactions have been observed with homo-
6
and heterotrinuclear clusters, there seems to have been
no report on related chemistry involving tetrahedral
mixed-metal carbonyl clusters. Here we present a study
on the reactivity of 1a and 1b toward PCyH2 which led
to unprecedented metallosite selectivity and the char-
acterization of metal core rearrangements leading to
new tri- and pentanuclear clusters.
Resu lts a n d Discu ssion
under catalytic conditions has rarely been determined.
For these tetrahedral clusters, stepwise addition of
monophosphine ligands may lead to the incorporation
of up to three ligands. Carbonyl substitution readily
takes place, and the interplay between the changes in
kinetic and thermodynamic parameters resulting from
phosphine substitution generally leads to complete
chemo- and stereoselectivity. Thus, previous studies
with 1a and 1b have shown that CO monosubstitution
by tertiary or secondary phosphine ligands takes place
exclusively at one of the three equivalent Co atoms. The
combined use of spectroscopic methods in solution, such
The reaction of HMCo3(CO)12 (1a , M ) Fe; 1b, M )
Ru) with 1 equiv of PCyH2 in dichloromethane at room
temperature led to the formation of HMCo3(CO)11-
(
PCyH2) (2a , M ) Fe; 2b, M ) Ru), which were charac-
terized by analytical and spectroscopic data (Table 1).
As reported earlier, the reactions of 1a and 1b with
various tertiary or secondary phosphines lead to mono-
substituted derivatives, in which the phosphine ligand
2
is always axially bound to a cobalt center. Variation
in the nature of the phosphine ligand results only in
slight changes in the IR patterns of the products.
Although the IR spectra in the ν(CO) region of cobalt-
substituted FeCo3 and RuCo3 clusters of the type
HMCo3(CO)11L are always very similar, the IR spectra
of 2a and 2b showed notable differences which point to
the presence of two isomers (Scheme 2). The Fe-
1
31
1
59
as H, P{ H}, and Co NMR, with solid-state studies
3
1
1
59
by P{ H} and Co NMR and X-ray diffraction allows
a better monitoring of the reactions and an understand-
ing of the selectivity for apical vs basal substitution,
which in the latter case may occur in an axial or
equatorial position (Scheme 1).
Sch em e 2
In such monosubstituted clusters, all observations so
far indicate that the phosphorus ligand is bound to
cobalt in an axial position. Disubstitution only leads to
the axial [Co, Co] isomer of HMCo3(CO)10L2 (L )
phosphine), whereas both [Co, Co] and [Co, Ru] isomers
may be observed in the case of 1b, depending on the
nature of the phosphine used:
Trisubstitution of 1a with P(OMe)3 has been established
by X-ray and neutron diffraction to occur at the cobalt
4
centers (one phosphite on each cobalt center). In the
reaction products of 1b with various phosphines, one
2
c,5
of the three ligands is always bonded to ruthenium.
The affinity toward phosphines decreases in the order
Co > Ru > Fe.
The majority of such studies have been concerned
with tertiary phosphines, and whereas there have been
a few examples dealing with the reactivity of secondary
phosphines, relatively little is known about the behavior
of primary phosphines PRH2. The latter ligands could
lead to simple CO substitution or formation of organo-
phosphido- (µ-PRH) or phosphinidene-based (µ3-PR)
containing cluster 2a was spectroscopically character-
ized as the axially Co-bound isomer, by analogy with
the data for HFeCo3(CO)11(PPh2H), the structure of
which has been established by X-ray diffraction.2a The
(
6) (a) Natarajan, K.; Zsolnai, L.; Huttner, G. J . Organomet. Chem.
1
981, 220, 365. (b) Iwasaki, F.; Mays, M. J .; Raithby, P. R.; Taylor, P.
L.; Wheatley, P. J . J . Organomet. Chem. 1981, 213, 185. (c) Field, J .
S.; Haines, R. J .; Smit, D. N. J . Organomet. Chem. 1982, 224, C49. (d)
Field, J . S.; Haines, R. J .; Smit, D. N. J . Organomet. Chem. 1986, 304,
C17. (e) Roland, E.; Bernhardt, W.; Vahrenkamp, H. Chem. Ber. 1986,
119, 2566.
(
4) (a) Huie, B. T.; Knobler, C. B.; Kaesz, H. D. J . Am. Chem. Soc.
978, 100, 3059. (b) Teller, R. G.; Wilson, R. D.; McMullan, R. K.;
Koetzle, T. F.; Bau, R. J . Am. Chem. Soc. 1978, 100, 3071.
5) Bouherour, S.; Braunstein, P.; Ros e´ , J ., unpublished results.
1
(

4
910 Organometallics, Vol. 18, No. 24, 1999
Ta ble 1. Selected IR a n d NMR Da ta
Bouherour et al.
3
1
1
59
P{ H} NMR δ,
ppm (∆1/2, Hz)d
Co NMR δ, ppm
1
1H NMR δ, ppmd
-21.5 (s, µ3-H)
d
cluster
IR ν(CO), cm-
(∆1/2, Hz)
HFeCo3(CO)12 (1a )
2060 vs, 2052 vs, 2030 m,
-2720 (420, Co-CO)e
c
1
990 m, 1887 s
HFeCo3(CO)11(PCyH2)
2080 m, 2036 vs, 2016 s,
-21.4 (s, µ3-H), 1.24 and
-40 (s, P-Co, 3200) -2719 (1800, 2 Co-CO),
-2674 (1800, 1 Co-P)
(Co) (2a )
1977 m, 1902 w, 1874 m,
1.80 (2 m, 11H, Cy), 3.2
c
1
1
860 m
(dd, PH2, 2H, J P-H ) 330
3
Hz, J H-H ) 5 Hz)
HFeCo3(CO)10(PCyH2)2 2061 s, 2022 vs, 2003 vs,
Co, Co) (3a ) 1966 m, 1863 w, 1854 m,
-21.9 (s, µ3-H), 1.32 and
-38 (m, P-Co, 2800) -2727 (1970, Co-CO),
-2629 (1350, Co-P)
(
1.82 (2 m, 11H, Cy), 3.72
a
1
1
839 m
(dd, PH2, 2H, J P-H ) 312
4
Hz, J P-H ) 56 Hz)
FeCo2(µ3-PCy)(CO)9
5a )
2092 m, 2047 vs, 2037 vs,
483 (s, µ3-P, 410)
-19.7 (s, P-Ru, 50)
-23.4 (d, P-Ru,
-2957 (10 000)
(
2030 vs, 2010 w, 2006 sh,
a
1
981 m, 1967 m
c
HRuCo3(CO)12 (1b)
HRuCo3(CO)11(PCyH2) 2078 m, 2043 s, 2028 s,
Ru) (2b) 1985 m, 1880 m, 1868 m
2067 vs, 2024 m, 1879 m
-19.7(s, µ3-H)
-2760 (1700, Co-CO)
-2790 (8300, Co-CO)
-18.2 (µ3-H), 0.9, 1.27, and
c
(
1.90 (3 m, 11H, Cy),
1
4
3
.33 (dd, PH2, 2H, J P-H )
3
54 Hz, J H-H ) 5 Hz)
HRuCo3(CO)10(PCyH2)2 2054 s, 2014 vs, 1970 m,
-18.6 (s, µ3-H), 0.8-0.9,
-2774 (5750, Co-CO +
Co-P)
c
3
(Co, Ru) (3b)
1850 m, 1835 sh
1.52-1.8, (3 m, 22H, Cy),
J P-P ) 50 Hz),
1
4
3
(
.0 (d, PH2, 2H, J P-H )
P-Co too broad
to be assigned
3
29 Hz, J H-H ) 5 Hz), 4.3
1
d, PH2, 2H, J P-H ) 350
3
Hz, J H-H ) 11 Hz)
RuCo4(µ4-PCy)(CO)13
4b)
2088 w, 2054 vs, 2036 sh,
too unstable
-1805 (7000, Co-CO +
Co-P)
(
2033 vs, 2020 w, 2012 w,
a
1
987 w, 1867 m
RuCo2(µ3-PCy)(CO)9
5b)
2091 s, 2049 vs, 2043 vs,
1.6, 1.96, and 2.35 (3m,
11H, Cy)
450 (s, µ3-P, 530)
too unstable
-3030 (10 000)
(
2028 vs, 2026 m, 2009 m,
a
1
980 m
HRuCo3(CO)10(PCyH2)- 2049 m, 1999 vs, 1985 sh,
NMe3) (Co, Ru) (6b) 1964 s, 1941 s, 1868 m,
too unstable
-2780 (6800, Co-CO),
-1360 (3400, Co-N),
-1150 (4000, Co-N)
(
b
1
846 s, 1824 s
a
In hexane. b In KBr. c In CH2Cl2. d In CDCl3. e In CD2Cl2.
situation appears different for the Ru-containing cluster
The reactions of 1a and 1b with more than 2 equiv of
PCyH2 led to the formation of the disubstituted com-
pounds HMCo3(CO)10(PCyH2)2 (3a , M ) Fe; 3b, M )
Ru). An interesting feature is that only the [Co, Co]
isomer of 3a was obtained, whereas 3b was found
exclusively as the [Co, Ru] isomer. This was established
by comparison of their IR and multinuclear NMR data
1
31
1
59
2
b and, on the basis of H, P{ H}, and Co NMR data
(
see Table 1) and by comparison with the structurally
7
characterized cluster HRuCo3(CO)11(TeMe2), we sug-
gest that the phosphine is coordinated to the Ru atom
1
(
Scheme 2). Thus, the H NMR resonance for the
hydride ligand appears at δ -18.2, instead of ca. δ -20
to -22 in clusters of the type HRuCo3(CO)11L or
HRuCo3(CO)10L2 in which the ligand(s) L is bound to
cobalt. Furthermore, the sharp 31P{ H} NMR resonance
of 2b contrasts with the quadrupole-broadened signals
2
a
with those of HFeCo3(CO)10(PPh2H)2 and HRuCo3-
(CO)10(PMe2Ph)2 (see Table 1). Thus, the 1H NMR
resonance for the hydride ligand in 3b appears at δ
-18.6 ppm, instead of δ -21.9 ppm in 3a . The sharp
2c
1
3
a
31
1
associated with cobalt-bound phosphorus nuclei. Fi-
P{ H} NMR doublet for the Ru-bound P nucleus of 3b
5
9
nally, the Co NMR spectrum of 2b consists of a broad
resonance at δ -2790 ppm, whereas for 2a , the expected
two resonances are observed at δ -2719 ppm (Co-CO)
and δ -2674 ppm (Co-P), in a 2:1 ratio.
is absent in 3a , where only a broad resonance is
observed at δ -40 ppm for the Co-bound P nuclei. These
observations are consistent with previous results con-
cerning the reaction of the Ru-bound telluride compound
HRuCo3(CO)11(TeMe2) with PMe2Ph, which yielded only
These features distinguish 2b from all the other
known phosphine-monosubstituted RuCo3 clusters, where
Co is always the preferred coordination site, with the
exception of RuCo3(CO)11(PMe2Ph)(µ3-AuPPh3), in which
the phosphine ligand PMe2Ph was established by X-ray
2
c
the disubstituted [Co, Ru] isomer. For other clusters
of the type HRuCo3(CO)10(Phosphine)2, the structure of
the preferred isomer depends on the nature of the
phosphine. With, for example, PPh3, the [Co, Co] isomer
first formed was stable, whereas with, for example,
PMe2Ph or Ph2PCH2C(O)Ph, the [Co, Co] kinetic isomer
8
diffraction to be bound to Ru. In this case, however,
steric effects might be at work. Thus, the bulky group
AuPPh3 may destabilize a phosphine bound to a Co
atom and trigger its migration to Ru, whereas with the
smaller hydride ligand, which is also µ3-bound to the
cobalt face in the related HRuCo3(CO)11(PMe2Ph), the
expected isomer with the phosphine bound to Co was
characterized by X-ray diffraction.9
2
c,5
slowly isomerized into the [Co, Ru] isomer.
Isolated 2b slowly transforms at room temperature
in CH2Cl2 solution, more rapidly in THF, into two new
species (a black and a yellow compound), as indicated
by analytical thin-layer chromatography and monitoring
59
by IR spectroscopy in the ν(CO) region or by Co NMR
spectroscopy (Scheme 3). The black species was found
(
7) Rossi, S.; Pursiainen, J .; Pakkanen, T. A. J . Organomet. Chem.
990, 397, 81.
8) Kakkonen, H. J .; Ahlgren, M.; Pakkanen, T. A. Acta Crystallogr.
994, C50, 528.
1
1
(
(9) Pursiainen, J .; Ahlgren, M.; Pakkanen, T. A.; Valkonen, J . J .
Chem. Soc., Dalton Trans. 1990, 1147.

Metallosite Selectivity Studies
Sch em e 3
Organometallics, Vol. 18, No. 24, 1999 4911
provide a fourth hydrogen and the Co(CO)2 fragment
necessary to complete the transformation of 2b into 4b,
a 1:1 mixture of pure 1b and 2b was stirred in CH2Cl2
2
2
at room temperature for up to 7 days. We found that
the presence of 1b did not affect the course of the
transformation of 2b. When Co2(CO)8 was added to 2b
in CH2Cl2, the formation of the mixture 4b + 5b was
slowed, until all Co2(CO)8 had been converted into Co4-
(CO)12. At this moment, the transformation of 2b
followed the normal course.
A similar behavior was observed with the iron-
containing cluster 2a , but in this case the formation of
the intermediate condensation product FeCo4(µ4-PCy)-
(µ-CO)2(CO)11 (4a ) was only detected using thin-layer
chromatography and identified by comparison with 4b.
This unstable compound rapidly transforms into the
phosphinidene-capped cluster FeCo2(µ3-PCy)(CO)9 (5a ),
which was characterized by comparison with FeCo2(µ3-
1
0
PPh)(CO)9. The latter was prepared in a low yield
2.5%) by a completely different method, the reaction
(
of PhP[Co(CO)4]2 with Fe2(CO)9.
Although the details of the mechanism leading to
elimination of hydrogen are not known, it is reasonable
to assume that the transformations leading to 4 and 5
involve initial P-H activation and CO substitution
processes, giving MCo3(µ-H)2(µ-PCyH)(CO)10 and finally
MCo3(µ-H)3(µ3-PCy)(CO)9. Unfortunately, none of the
expected intermediates has so far been observed. How-
ever, this hypothesis of stepwise P-H oxidative-addition
reactions of a monosubstituted compound has been
verified with the trinuclear clusters Os3(CO)11(PRH2).6a
The transformations of 2a or 2b may be easily
accelerated by reaction with trimethylamine N-oxide.
Thus, reaction of 2a with a stoichiometric amount of
Me3NO led to CO2 evolution and formation of a green
solution characteristic for a disubstituted cluster. After
a few minutes, the color of this solution rapidly turned
deep red and the presence of cluster 5a was indicated
by TLC, together with a green spot attributed to
HFeCo3(CO)10(NMe3)(PCyH2) by analogy with the known
to be a condensation product, the pentanuclear cluster
RuCo4(µ4-PCy)(µ-CO)2(CO)11 (4b), which has been struc-
turally characterized by X-ray diffraction (see below).
Such a cluster expansion reaction has been previously
observed in the reaction of Ru3(CO)12 with PPhH2, which
afforded tetranuclear and pentanuclear phosphinidene-
capped homometallic clusters.6 On the other hand, the
yellow compound was found to be a heterometallic
trinuclear cluster and characterized by X-ray diffraction
as RuCo2(µ3-PCy)(CO)9 (5b). This cluster results for-
mally from the loss of two 12-valence-electron (12-VE)
2a
59
HFeCo3(CO)10(NMe3)(PPh2H). However, Co NMR
monitoring of this reaction did not allow observation of
the resonance of the amine-substituted cobalt atom. The
reaction of 2b with Me3NO afforded the unstable
phosphine-amine disubstituted cluster HRuCo3(CO)10-
c
(NMe3)(PCyH2) (6b), which was separated from decom-
position products by extraction in nonpolar solvents
such as toluene. Cluster 6b was identified as the [Co,
Ru] isomer, where the phosphine has remained on Ru
and the amine ligand has substituted a Co-bound CO.
This identification was done by comparison of its IR and
+
fragments Co(CO)2 from 4b. The analogous clusters
RuCo2(µ3-PR)(CO)9 (R ) Me, Ph) have been obtained by
reaction of RuCo2(CO)11 with PRH2 but were not char-
acterized by X-ray diffraction.6
59
Co NMR data with those of the phosphine disubsti-
tuted cluster HRuCo3(CO)10(PMe2Ph)2, in which the [Co,
e
2c
Co] and [Co, Ru] isomers can be readily differentiated.
At the beginning of the transformation of 2b, 5b is
only present in minor quantities compared to 4b. This
situation reverses with time, ending with complete
conversion of 4b. When pure 4b was dissolved in CH2-
Cl2 or THF, it rapidly formed 5b, which was the only
species detected by 59Co NMR spectroscopy, and some
decomposition product that did not migrate on TLC
plates (Scheme 3). This strongly suggests, but of course
does not prove, that 5b is formed via the intermediacy
of 4b and is not formed directly from 2b. To see whether
a bimolecular process, where a molecule of 1b would
However, when the reaction of 2b with Me3NO was
performed in an NMR tube for direct monitoring by
59
Co NMR, two new resonances were observed at δ
-
1150 ppm and -1360 ppm which are typical for amine-
2b
substituted Co atoms. This may be explained by
assuming that, in solution, this unstable cluster isomer-
izes, at least in part, to give a mixture of [Co, Co] and
[
Co, Ru] isomers (eq 1). For comparison, a similar
59
sensitivity of the Co NMR resonance of an amine-
(10) Burt, J . C.; Schmid, G. J . Chem. Soc., Dalton Trans. 1978, 1385.

4
912 Organometallics, Vol. 18, No. 24, 1999
Bouherour et al.
substituted Co nucleus to the presence of a phosphine
on an adjacent cobalt has been previously observed on
going from the [Co, Co] isomer of HFeCo3(CO)10(NMe3)-
(
PPh2H) (δ -780 ppm) to HFeCo3(CO)11(NMe3) (δ -910
2
a
ppm).
The existence of 6b supports our previous suggestion
that the reaction of HRuCo3(CO)11(PMe2Ph) with Me3-
NO occurs via a short-lived intermediate in which the
phosphine has migrated to Ru.2 The mixture of 6b and
c
7
b transforms rapidly in solution (t1/2 ) 30 min) into
first 4b and 5b and eventually pure 5b, as shown by
5
9
Co NMR spectroscopy, where the two additional
resonances at δ -1805 and -3030 ppm grew at the
expense of those at δ -1150 and -1360 ppm, reflecting
the displacement of the Co-bound amine ligand.
4 4
F igu r e 1. ORTEP view of one molecule of RuCo (µ -PCy)-
(µ-CO) (CO) (4b) with the atom-labeling scheme (50%
2
11
Cr yst a l St r u ct u r es of R u Co (µ4-P Cy)(µ-CO)2-
probability ellipsoids).
4
(
CO)11 (4b) a n d Ru Co2(µ3-P Cy)(CO)9 (5b). The mo-
lecular structures of 4b and 5b have been determined
by X-ray diffraction and are shown in Figures 1 and 2.
Selected bond distances and angles are given in Tables
2
and 3, respectively.
In cluster 4b the two crystallographically independent
molecules in the asymmetric unit are structurally
equivalent and are almost related to each other by a
mirror plane, except for a slight rotation of the Cy
substituent. The overall cluster geometry consists of a
distorted octahedron with a cobalt atom and a phos-
phorus atom on opposite apexes, while the other four
metal atoms form an approximately square-planar
RuCo3 array (Figure 1). Two Co-Co bonds are sym-
metrically bridged by a CO ligand, and the Co-Co
distances range from Co(1)-Co(3) ) 2.493(2) Å to Co-
(2)-Co(3) ) 2.598(2) Å (molecule A). The other carbonyl
ligands are terminally bound, two on each cobalt and
three on ruthenium. The phosphinidene ligand caps the
RuCo3 plane in a slightly asymmetric manner such that
one of the Co-P distances is shorter than the other two
(
(
(
see Table 2). The Ru-P(1) distance of 2.305(3) Å (2.273-
3) Å in molecule B) is shorter than in the cluster Ru5-
µ4-PPh)(CO)15 (2.339(6)-2.407(7) Å).11 The P(1)-C(14)
2 3
F igu r e 2. ORTEP view of one molecule of RuCo (µ -PCy)-
distance of 1.85(1) Å (1.89(1) Å in molecule B) involving
the phosphinidene ligand is comparable to that previ-
ously reported in the only other structurally character-
ized cluster with a µ4-PCy ligand, Ru4(µ4-PCy)2(µ-
PCy2)2(CO)8.12 Cluster 4b has 7 electron pairs, consistent
with a nido octahedron for the five metal atoms or a
closo octahedron when the P atom is considered as part
of the skeleton. The metal atoms all obey the 18-electron
rule.
(
CO)
9
(5b) with the atom-labeling scheme (50% probability
ellipsoids).
ruthenium atom is statistically disordered over all three
1
metal sites with a pseudo atom named RC (RC ) /3 Ru
2
+
/3 Co) representing this metal site (Figure 2). Related
disorder problems have been encountered with H2-
1
3
RuOs3(CO)13 and (AsPh4)[H3RuOs3(CO)12]. The aver-
age metal-metal bond distance of 2.648 Å is interme-
diate between a Co-Co and a Ru-Co bond length in
b. Each metal atom bears three terminal carbonyl
groups. As in FeCo2(µ3-PPh)(CO)9, the phosphorus
Cluster 5b contains a triangular core with one
ruthenium and two cobalt atoms. The position of the
4
1
4
(
11) Natarajan, K.; Zsolnai, L.; Huttner, G. J . Organomet. Chem.
981, 209, 85.
12) Beguin, A.; Rheinwald, G.; Stoeckli-Evans, H.; S u¨ ss-Fink, G.
Helv. Chim. Acta 1994, 77, 525.
1
(
(13) Rheingold, A. L.; Gates, B. C.; Scott, J . P.; Budge, J . R. J .
Organomet. Chem. 1987, 331, 81.

Metallosite Selectivity Studies
Organometallics, Vol. 18, No. 24, 1999 4913
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles (d eg) for Ru Co
molecule
4
(µ
4
-P Cy)(µ-CO)
2
(CO)11 (4b)
molecule
A
B
A
B
Bond Distances
Ru(1)-Co(1)
Ru(1)-Co(2)
Ru(1)-Co(4)
Ru(1)-P(1)
Ru(1)-C(1)
Ru(1)-C(2)
Ru(1)-C(3)
Co(1)-Co(3)
Co(1)-Co(4)
Co(1)-P(1)
Co(1)-C(4)
Co(1)-C(5)
Co(1)-C(6)
Co(2)-Co(3)
2.771(2)
2.707(2)
2.699(2)
2.305(3)
1.91(1)
1.89(1)
1.97(1)
2.493(2)
2.498(2)
2.252(3)
1.76(1)
2.684(2)
2.677(2)
2.666(2)
2.273(3)
1.88(2)
1.93(2)
1.88(2)
2.553(2)
2.499(2)
2.236(3)
1.80(1)
1.72(1)
2.24(2)
2.638
Co(2)-Co(4)
Co(2)-P(1)
Co(2)-C(7)
Co(2)-C(8)
Co(2)-C(9)
Co(3)-Co(4)
Co(3)-P(1)
Co(3)-C(6)
Co(3)-C(10)
Co(3)-C(11)
Co(4)-C(9)
Co(4)-C(12)
Co(4)-C(13)
P(1)-C(14)
2.533(2)
2.241(3)
1.76(1)
1.76(2)
1.92(1)
2.557(2)
2.204(3)
1.87(1)
1.79(1)
1.80(2)
1.99(1)
1.80(1)
1.83(1)
1.85(1)
2.535(2)
2.256(3)
1.76(1)
1.74(2)
1.90(1)
2.605(2)
2.238(3)
1.87(1)
1.80(1)
1.82(1)
1.98(1)
1.80(1)
1.77(2)
1.89(1)
1.76(1)
1.88(1)
2.598(2)
Bond Angles
Co(1)-Ru(1)-Co(2)
Co(1)-Ru(1)-P(1)
Co(2)-Ru(1)-P(1)
Co(4)-Ru(1)-P(1)
P(1)-Ru(1)-C(1)
P(1)-Ru(1)-C(2)
P(1)-Ru(1)-C(3)
Ru(1)-Co(1)-Co(3)
Ru(1)-Co(1)-Co(4)
Ru(1)-Co(1)-P(1)
Co(3)-Co(1)-Co(4)
Co(3)-Co(1)-P(1)
Co(3)-Co(1)-C(6)
Co(4)-Co(1)-P(1)
P(1)-Co(1)-C(4)
P(1)-Co(1)-C(5)
P(1)-Co(1)-C(6)
Ru(1)-Co(2)-Co(3)
Ru(1)-Co(2)-Co(4)
Ru(1)-Co(2)-P(1)
Co(3)-Co(2)-Co(4)
Co(3)-Co(2)-P(1)
83.89(5)
51.69(8)
52.37(8)
73.91(8)
119.0(4)
94.7(3)
144.0(4)
92.35(6)
61.36(5)
53.43(8)
61.65(6)
55.07(8)
48.1(4)
78.91(9)
101.6(4)
150.1(4)
99.6(5)
91.55(6)
61.90(5)
54.56(8)
59.77(6)
53.57(8)
85.88(6)
52.84(8)
53.48(8)
75.47(9)
110.7(6)
90.8(4)
Co(4)-Co(2)-P(1)
P(1)-Co(2)-C(7)
P(1)-Co(2)-C(8)
P(1)-Co(2)-C(9)
Co(1)-Co(3)-Co(2)
Co(1)-Co(3)-Co(4)
Co(1)-Co(3)-P(1)
Co(1)-Co(3)-C(6)
Co(2)-Co(3)-Co(1)
Co(2)-Co(3)-Co(4)
Co(2)-Co(3)-P(1)
Co(4)-Co(3)-P(1)
P(1)-Co(3)-C(6)
P(1)-Co(3)-C(10)
P(1)-Co(3)-C(11)
Ru(1)-Co(4)-Co(1)
Ru(1)-Co(4)-Co(2)
Ru(1)-Co(4)-Co(3)
Co(1)-Co(4)-Co(2)
Co(1)-Co(4)-Co(3)
Co(2)-Co(4)-Co(3)
Co(1)-Co(4)-C(9)
78.4(1)
110.0(5)
119.4(4)
128.9(4)
91.89(9)
59.27(8)
56.9(1)
78.49(9)
111.5(4)
114.8(5)
128.8(4)
89.42(7)
57.95(6)
55.17(9)
58.4(5)
89.42(7)
57.83(5)
54.37(9)
77.33(9)
107.7(5)
148.1(4)
96.1(5)
62.52(7)
61.89(6)
92.32(6)
93.03(7)
59.98(7)
61.75(5)
140.1(4)
150.3(4)
93.8(7)
48.5(4)
61.80(6)
54.10(9)
62.07(6)
55.25(9)
45.4(4)
79.65(9)
106.8(4)
150.8(4)
96.1(4)
91.33(6)
61.46(6)
54.05(8)
60.42(5)
53.74(9)
91.95(7)
58.84(6)
54.89(9)
78.50(9)
101.7(4)
154.6(5)
97.0(4)
64.30(5)
62.22(5)
92.63(6)
93.40(7)
59.07(6)
61.39(6)
140.9(4)
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
is comparable to those observed in other µ3-PR lig-
(
d eg) for Ru Co
2
(µ
3
-P Cy)(CO)
9
(5b)
6b,14
ands.
Cluster 5b has 6 electron pairs, consistent
Bond Distances
with an arachno trigonal bipyramid for the three metal
atoms or a nido trigonal bipyramid when the P atom is
considered as part of the skeleton. As in 4b, the metal
atoms all obey the 18-electron rule.
RC(1)-RC(2)
RC(1)-RC(3)
RC(2)-RC(3)
RC(1)-P(1)
RC(2)-P(1)
RC(3)-P(1)
RC(1)-C(1)
RC(1)-C(2)
2.641(2)
2.647(1)
2.655(1)
2.180(2)
2.173(1)
2.176(1)
1.812(5)
1.823(5)
RC(1)-C(3)
RC(2)-C(7)
RC(2)-C(8)
RC(2)-C(9)
RC(3)-C(4)
RC(3)-C(5)
RC(3)-C(6)
P(1)-C(10)
1.818(5)
1.842(5)
1.839(5)
1.825(5)
1.820(5)
1.849(6)
1.834(5)
1.836(4)
Con clu sion
We have observed that monosubstitution of HMCo3-
Bond Angles
RC(2)-RC(1)-RC(3) 60.26(4) RC(3)-RC(2)-P(1)
RC(2)-RC(1)-P(1) 52.53(4) RC(3)-RC(2)-C(7)
RC(2)-RC(1)-C(1) 151.8(2) RC(3)-RC(2)-C(8)
(CO)12 with PCyH2 occurs with a different metallose-
52.43(4)
98.0(2)
97.7(2)
lectivity as a function of M ) Fe, Ru. In the former case,
substitution of a Co-bound CO ligand occurs, whereas
when M ) Ru, the phosphine ligand is bound to Ru.
This reaction appears to be under thermodynamic
control. Introduction of a second substituent (PCyH2 or
NMe3) occurs in both cases at cobalt and, in the case of
HFeCo3(CO)11(PCyH2), at a cobalt that does not carry
the PCyH2 substituent. The clusters HMCo3(CO)11-
RC(2)-RC(1)-C(2)
RC(2)-RC(1)-C(3)
RC(3)-RC(1)-P(1)
RC(3)-RC(1)-C(1)
97.4(2) RC(3)-RC(2)-C(9) 153.1(2)
96.4(2) RC(1)-RC(3)-RC(2) 59.77(3)
52.51(4) RC(1)-RC(3)-P(1)
96.8(2) RC(1)-RC(3)-C(4)
52.64(5)
98.7(2)
96.5(2)
RC(3)-RC(1)-C(2) 152.1(2) RC(1)-RC(3)-C(5)
RC(3)-RC(1)-C(3)
96.4(2) RC(1)-RC(3)-C(6) 153.7(2)
RC(1)-RC(2)-RC(3) 59.98(4) RC(2)-RC(3)-P(1)
52.34(4)
RC(1)-RC(2)-P(1)
RC(1)-RC(2)-C(7)
52.76(4) RC(2)-RC(3)-C(4) 153.4(2)
(PCyH2) (2a , M ) Fe; 2b, M ) Ru) transform in solution
96.4(2) RC(2)-RC(3)-C(5)
97.4(2)
98.4(2)
to give the corresponding µ3-phosphinidene-capped het-
erotrinuclear clusters MCo2(µ3-PCy)(CO)9 (5a , M ) Fe;
RC(1)-RC(2)-C(8) 153.7(2) RC(2)-RC(3)-C(6)
RC(1)-RC(2)-C(9)
98.8(2)
5
b, M ) Ru). When M ) Ru, a pentanuclear intermedi-
atom of the µ3-phosphinidene ligand caps symmetrically
the trimetal plane with an average RC-P(1) bond
distance of 2.176 Å which is significantly shorter than
the Co-P or Ru-P bond distances in cluster 4b. As
expected, the µ3-P(1)-C(10) distance of 1.836(4) Å is
slightly shorter than the µ4-P-C(14) distance in 4b and
ate could be isolated and characterized by X-ray dif-
fraction as the µ4-phosphinidene-capped cluster RuCo4-
(µ4-PCy)(µ-CO)2(CO)11 (4b). The analogous species could
(14) Beurich, H.; Madach, T.; Richter, F.; Vahrenkamp, H. Angew.
Chem., Int. Ed. Engl. 1979, 18, 690.

4
914 Organometallics, Vol. 18, No. 24, 1999
Bouherour et al.
not be isolated when M ) Fe, owing to its lability. The
transformation of 2a ,b was accelerated by addition of
Me3NO, which generated a labile phosphine-amine
intermediate. We believe that a significant aspect of this
work is the demonstration that a reaction which rep-
resents a cluster partial fragmentation, with nuclearity
change from 4 to 3, may occur via the intermediacy of
a larger cluster, of nuclearity 5. This observation may
bear relevance to a number of rearrangement processes
in cluster chemistry and be more general than previ-
ously thought.
mL), PCyH
2
(0.043 mL, 0.326 mmol) was added, and the
solution was stirred at room temperature. The reaction was
monitored by TLC plates, which indicated the formation of two
major products: the monosubstituted 2b followed by the
disubstituted compound 3b. After being stirred for 2 h, the
dark red solution was filtered and the solvent evaporated in
vacuo. Chromatographic separation, with hexane/CH
2 2
Cl (80/
2
0) as eluant, yielded pure 3b (0.035 g, 27%). However, this
compound was highly unstable in the solid state as well as in
solution.
Prolonged reaction times or the use of an excess of PCyH2
did not improve the yield and favored the formation of a new
compound (probably a trisubstituted derivative not further
investigated) together with some decomposition.
Exp er im en ta l Section
P r ep a r a tion of Ru Co
Co (CO)12 (1b; 0.320 g, 0.520 mmol) was dissolved in CH
(30 mL), and PCyH (0.069 mL, 0.520 mmol) was added. After
4
(µ
4
-P Cy)(µ-CO)
2
(CO)11 (4b). HRu-
Gen er a l P r oced u r es. Reactions and manipulations, except
3
2
Cl
2
chromatographic separations, were carried out under N
2
using
2
standard Schlenk tube techniques. Solvents were distilled
the solution was stirred for 0.5 h at room temperature, the
solution was filtered and the solvent was evaporated in vacuo.
The resulting solid was extracted with toluene (30 mL), and
this solution was placed at -15 °C. After 1 week the toluene
1
5
2a
before use. HFeCo
according to published procedures. PCyH
3
(CO)12 and HRuCo
3
(CO)12 were prepared
was commercially
2
available and used as received. Solution infrared spectra were
recorded on a Nicolet 20SXC or a Bruker IFS-66 FT IR spec-
2 2
was evaporated; the solid residue was dissolved in CH Cl (20
1
31
1
trometer. H and P{ H} NMR spectra were recorded at
00.17 and 121.5 MHz, respectively, on a Bruker AC-300
spectrometer using CDCl as the solvent. Chemical shifts are
relative to TMS and H PO
were measured on a Bruker MSL-300 instrument (71.21 MHz).
mL) and this solution stored 1 week at room temperature. The
presence of two new products together with the monosubsti-
tuted compound 2b was indicated by TLC. The solvent was
evaporated, and the solid residue was extracted with hexane.
The resulting solution was placed at -15 °C overnight, giving
3
3
5
9
3
4
, respectively. Co NMR spectra
5
9
The chemical shifts reported (ppm) for Co are positive high
frequency from the external reference K [Co(CN) ] saturated
in D O. Standard parameters are as follows: pulse width 3
µs, sweep width 263 kHz, number of scans between 5000 and
00 000. Selected physical and spectroscopic data for the com-
black needles of 4b (0.080 g, 19%) Anal. Calcd for C19
4 13
H11Co O -
3
6
PRu: C, 28.00; H, 1.36. Found: C, 28.5, H, 1.4. FAB-MS: m/z
+
+
+
2
815 (10%, M ), 787 (74%, M - CO), 759 (100%, M - 2CO),
+
+
+
731 (96%, M - 3CO), 703 (52%, M - 4CO), 675 (45%, M
-
1
5CO).
plexes are given in Table 1. When the product stability
allowed, elemental analyses are given. The progress of the
reactions was monitored by analytical thin-layer chromatog-
raphy (5554 Kieselgel 60F254, Merck), and the products were
separated on 20 × 20 cm glass plates coated with Kieselgel
P r ep a r a tion of F eCo (µ -P Cy)(CO) (5a ). HFeCo (CO) -
2
3
9
3
11
(PCyH ) (2a ; 0.050 g, 0.076 mmol) was dissolved in THF (10
2
mL), and the solution was stirred at room temperature for 2
days. The progressive formation of a new brown-violet com-
pound was monitored by TLC. The solution was filtered, and
the solvent was evaporated in vacuo. The resulting solid was
extracted with hexane (10 mL), and this solution was placed
at -15 °C for 2 days, giving black crystals of 5a (0.024 g, 58%).
6
0F254.
P r ep a r a tion of HF eCo
CO)12 (1a ; 0.331 g, 0.581 mmol) was dissolved in CH
3
(CO)11(P CyH
2
) (2a ). HFeCo
Cl (40
(0.077 mL, 0.581 mmol) was added. After the
3
-
(
2
2
mL), and PCyH
2
Anal. Calcd for C15
33.7; H, 2.5.
2 9
H11Co FeO P: C, 33.34; H, 2.05. Found: C,
mixture was stirred for 0.5 h at room temperature, the dark
violet solution was filtered and the solvent was evaporated in
vacuo. The resulting solid was extracted with hexane (40 mL),
and this solution was placed at -15 °C overnight, giving black
P r ep a r a tion of Ru Co (µ -P Cy)(CO) (5b). HRuCo (CO) -
2
3
9
3
11
(PCyH ) (2b; 0.050 g, 0.071 mmol) was dissolved in THF (20
2
mL). The solution was stirred at room temperature. The
progressive formation of a new orange compound was moni-
tored by TLC. After 2 days, the resulting solution was
evaporated to dryness and the solid residue was extracted with
hexane. This solution, placed overnight at -15 °C, afforded
orange crystals of 5b (0.017 g, 42%). Anal. Calcd for C H11-
crystals of 2a (0.155 g, 45%). Anal. Calcd for C17
H
14Co
3
-
FeO11P: C, 31.04; H, 2.15. Found: C, 30.8; H, 2.2.
P r ep a r a tion of HRu Co
CO)12 (1b; 0.240 g, 0.390 mmol) was dissolved in CH
mL), and PCyH (0.052 mL, 0.391 mmol) was added. The wine
3
(CO)11(P CyH
2
) (2b). HRuCo
3
-
(
2
Cl
2
(20
2
1
5
red solution, which became immediately dark red, was stirred
for 0.5 h at room temperature. The solution was filtered, and
the solvent was evaporated in vacuo. The resulting solid was
extracted with hexane (20 mL), and this solution was placed
at -15 °C overnight, giving black crystals of 2b (0.170 g, 62%).
2 9
Co O PRu: C, 30.79; H, 1.90. Found: C, 31.0; H, 2.2. FAB-
+
+
+
MS: m/z 585 (40%, M ), 557 (100%, M - CO), 529 (80%, M
+
- 2CO), 501 (20%, M - 3CO).
Rea ction of HRu Co (CO) (P CyH ) w ith Me NO. Solid
3
11
2
3
Me NO was added to a solution of HRuCo (CO) (PCyH ) (1b;
3
3
11
2
Anal. Calcd for C17
C, 29.5; H, 2.1.
H
14Co
3
O
11PRu: C, 29.04; H, 2.01. Found:
0.040 g, 0.057 mmol) in CH Cl2 (10 mL). Evolution of CO2
2
occurred immediately, and the wine red solution became violet.
After the solution was stirred for 0.25 h at room temperature,
it was evaporated in vacuo. The resulting solid was extracted
with hexane (20 mL), and this solution was placed at -15 °C
for 12 h, giving black crystals of HRuCo (CO) (NMe ) (PCyH )
P r ep a r a tion of HF eCo
CO)12 (1a ; 0.231 g, 0.405 mmol) was dissolved in CH
mL), and PCyH (0.137 mL, 1.04 mmol) was added. After the
3
(CO)10(P CyH
2
)
2
(3a ). HFeCo
3
-
(
2
2
Cl (30
2
mixture was stirred for 1 h at room temperature, the TLC
plates indicated the formation of one major dark violet com-
pound. The solution was filtered, and the solvent was evapo-
rated in vacuo. The resulting oil was extracted with hexane
3
11
3
2
(6b; 0.020 g, 50%). Anal. Calcd for C H NCo O PRu: C,
1
9
23
3
10
31.08; H, 3.16; N, 1.91. Found: C, 31.6; H, 3.4; N, 2.1.
X-r a y Cr ysta llogr a p h y. Suitable black crystals of 4b and
(
60 mL), and this solution was placed at -15 °C overnight,
giving a black powder of 3a (0.162 g, 54%) Anal. Calcd for
: C, 35.42; H, 3.65. Found: C, 35.7, H, 3.8.
P r ep a r a tion of HRu Co (CO)10(P CyH (3b). HRuCo
CO)12 (1b; 0.100 g, 0.163 mmol) was dissolved in CH Cl (20
5
2 2
b were obtained by slow crystallization from a CH Cl /hexane
solution at -15 °C. Diffraction measurements were carried out
22 3 2
C H27Co FeO10P
at room temperature on an automatic Nonius CAD-4 diffrac-
)
2
3
-
tometer using graphite-monochromated Mo KR radiation.16
3
2
(
2
2
(
16) Fair, C. K. MolEN: An Interactive Intelligent System for Crys-
(15) Chini, P.; Colli, L.; Peraldo, M. Gazz. Chim. Ital. 1960, 90, 1005.
tal Structure Analysis; Enraf-Nonius, Delft, The Netherlands, 1990.

Metallosite Selectivity Studies
Organometallics, Vol. 18, No. 24, 1999 4915
ψ scan,19 the structure was solved with SIR-97, which revealed
Ta ble 4. Cr ysta llogr a p h ic Da ta for
Ru Co (µ -P Cy)(µ-CO) (CO)11 (4b) a n d
Ru Co (µ -P Cy)(CO) (5b)
2
0
4
4
2
the non-hydrogen atoms of the structure. After anisotropic
refinement, all the hydrogen atoms were found by a difference
Fourier synthesis. The whole structure was refined with
SHELXL97,21 by full-matrix least-squares techniques (use of
F magnitude; x, y, z, âij for Ru, Co, P, O, and C atoms and x,
y, z in riding mode for H atoms): 686 variables and 4565
2
3
9
4
b
5b
formula
fw
temp (K)
RuCo4C19H11O13P
815.06
RuCo2C15H11O9P
585.2
293(2)
293(2)
2
2
2
observations; w(calcd) ) 1/[σ (F
o
) + (0.1271P) ], where P )
wavelength (Å)
cryst syst
space group
a (Å)
0.71069
triclinic
P1h
0.71069
triclinic
P1h
2
2
(F
o
+ 2F
c
)/3 with the resulting R ) 0.055, R ) 0.164, and
GOF ) 1.075 (residual ∆F e 1.88 e Å ).
w
-
3
9.103(3)
16.425(2)
17.708(2)
91.12(1)
91.13(2)
99.66(2)
2609(1)
4
8.119(2)
8.124(6)
17.709(6)
86.34(3)
83.61(3)
63.52(4)
1039(1)
2
Com p ou n d 5b. Data collection parameters are given in
Table 4. 2θmax ) 54°, scan ω/2θ ) 1, and tmax ) 60 s; intensity
controls without appreciable decay (1.0%) give 4861 reflections,
of which 4530 were independent (3743 with I > 2σ(I)). After
Lorentz and polarization corrections and absorption corrections
with ψ scan,19 the structure was solved with SIR-97, which
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
3
V (Å )
2
0
revealed the non-hydrogen atoms of the structure. During
the calculations, the Ru and Co atoms appeared statistically
disordered; therefore, a pseudo atom named RC was created
Z
3
calcd density (Mg/m ) 2.075
1.871
2.411
572
-
1
abs coeff (mm
)
3.180
1584
1
2
F(000)
(RC ) /
3
3
Ru + / Co)). After anisotropic refinement, all the
cryst size (mm)
θ range for data
collecn (deg)
0.35 × 0.25 × 0.09 0.25 × 0.22 × 0.10
hydrogen atoms are found by a difference Fourier synthesis.
The whole structure was refined with SHELXL97, by full-
1.15-22.97
1.16-26.97
21
matrix least-squares methods (use of F magnitude; x, y, z, âij
for Ru, Co, P, O, and C atoms and x, y, z in riding mode for H
limiting indices
0 e h e 9,
0 e h e 10,
-9 e k e 10,
-22 e l e 22
4861/4530
-18 e k e 17,
-19 e l e 19
2
atoms): 255 variables and 3743 observations; w(calcd) ) 1/[σ -
2
2
2
2
(F
o
) + (0.0787P) + 0.8325P], where P ) (F
o
+ 2F
c
)/3 with
no. of rflns
7761/7218
collcd/unique
completeness to θmax 100.0
refinement method
(R(int) ) 0.0183)
(R(int) ) 0.0148)
the resulting R ) 0.039, R
(residual ∆F e 0.97 e Å ).
w
) 0.116, and GOF ) 1.069
-
3
100.0
full-matrix least squares on F2
no. of data/restraints/ 7218/0/686
params
4530/0/255
Ack n ow led gm en t. We are grateful to Prof. P.
Granger and Drs. J . Raya and T. Richert (Strasbourg,
goodness of fit on F2
final R indices
1.075
1.069
59
France) for their contribution to the Co NMR study
R1 ) 0.0551,
wR2 ) 0.1649
R1 ) 0.1167,
wR2 ) 0.1894
0.0000(2)
R1 ) 0.0389,
wR2 ) 0.1162
R1 ) 0.0529,
wR2 ) 0.1237
0.0067(13)
and to the CNRS, the Minist e` re de l′Education Natio-
nale, de l’Enseignement Sup e´ rieur et de la Recherche,
the Minist e` re des Affaires Etrang e` res (Paris), and the
Minist e` re des Affaires Etrang e` res (Alger) for support
of the Strasbourg-Constantine Cooperation Project 96
MDU 371.
(
I > 2σ(I))
R indices (all data)
extinction coeff
largest diff peak and 1.881 and -1.509
0.977 and -0.580
-
3
hole, e Å
The cell parameters are obtained by fitting a set of 25 high-θ
reflections. The intensities of three reflections were monitored
every 1 h of exposure and showed no evidence of decay. Crystal
data and intensity collection parameters are given in Table 4.
Atomic scattering factors were taken from ref 17. Ortep plots
were obtained using PLATON98. All the calculations were
performed on a Silicon Graphics Indy computer.
Str u ctu r e An a lysis a n d Refin em en t. Com p ou n d 4b.
Data collection parameters are given in Table 4. 2θmax ) 54°,
scan ω/2θ ) 1, and tmax ) 60 s; intensity controls without
appreciable decay (1.5%) give 7761 reflections, from which
Su p p or tin g In for m a tion Ava ila ble: Tables giving de-
tails of the structure determination, atomic coordinates,
including those of the hydrogen atoms, anisotropic thermal
parameters, and all bond distances and angles for complexes
4
b and 5b. This material is available free of charge via the
1
8
Internet at http://pubs.acs.org.
OM9902840
(19) Spek, A. L. HELENA: Program for the Handling of CAD4-
Diffractometer Output SHELX(S/L); Utrecht University, Utrecht, The
Netherlands, 1997.
(20) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G.; Gia-
7
218 were independent (4565 with I > 2σ(I)). After Lorentz
civazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna,
R. SIR97: a New Tool for Crystal Structure Determination and
Refinement. J . Appl. Crystallogr. 1998, 31, 7477.
and polarization corrections and absorption corrections with
(
17) International Tables for X-ray Crystallography; Kynoch Press:
Birmingham, U.K., 1974; Vol. IV, p 99.
18) Spek, A. L. PLATON: A Multipurpose Crystallographic Tool;
Utrecht University, Utrecht, The Netherlands, 1998.
(21) Sheldrick, G. M. SHELXL93: Program for the Refinement of
Crystal Structures; University of G o¨ ttingen, G o¨ ttingen, Germany,
1993.
(
(22) We are grateful to a reviewer for suggesting this experiment.