Synthesis and structures of (3-methyl-2-pyridyl)diphenylphosphane derivatives of metal clusters

Article abstract of DOI:10.1016/j.jorganchem.2004.01.006

An unsymmetric bidentate ligand (3-methyl-2-pyridyl)diphenylphosphane (P(Mepy)Ph₂) is able to react with various tetranuclear transition metal clusters such as HRuCo₃(CO)₁₂, HRuRh₃(CO)₁₂ and Rh₄(CO)₁₂. The synthesis and crystal structures of HRuCo₃(CO) ₁₀(P(Mepy)Ph₂) (1), HRuRh₃(CO) ₁₀(P(Mepy)Ph₂) (2), RuRh₂(CO) ₉(P(Mepy)Ph) (3) and Rh₆(CO)₁₄(P(Mepy) Ph₂) (4) are described. In 1, 2 and 4 the phosphane ligand replaces the carbonyls and acts as a bridging bidentate P-N group. The formation of 3 includes degradation of both the metal cluster core and the ligand itself. One of the P-C bonds in the ligand is cleaved and the ligand caps a metal triangle with a bridging phosphido group together with the nitrogen donor. The reaction between dinuclear Rh₂ (CO)₄Cl₂ and P(Mepy)Ph₂ gives a binuclear Rh₂(μ-CO)Cl₂(P(Mepy)Ph₂) ₂ (5) with bridging ligands in a head-to-tail arrangement. The crystal structure is also given.

Full text of DOI:10.1016/j.jorganchem.2004.01.006

Journal of Organometallic Chemistry 689 (2004) 1064–1070
www.elsevier.com/locate/jorganchem
Synthesis and structures of
(3-methyl-2-pyridyl)diphenylphosphane derivatives of metal clusters
a,
Sirpa Jaaskelainen , Matti Haukka , Helena Riihimaki ,
a
b
*
€€
Jouni T. Pursiainen , Tapani A. Pakkanen
€
€
b
a
a
Department of Chemistry, University of Joensuu, P.O. Box 111, Joensuu Fin-80101, Finland
b
Department of Chemistry, University of Oulu, P.O. Box 3000, Oulu Fin-90014, Finland
Received 5 September 2003; accepted 3 January 2004
Abstract
An unsymmetric bidentate ligand (3-methyl-2-pyridyl)diphenylphosphane (P(Mepy)Ph2) is able to react with various tetranuclear
transition metal clusters such as HRuCo3(CO)12, HRuRh3(CO)12 and Rh4(CO)12. The synthesis and crystal structures of
HRuCo3(CO)10(P(Mepy)Ph2) (1), HRuRh3(CO)10(P(Mepy)Ph2) (2), RuRh2(CO)9(P(Mepy)Ph) (3) and Rh6(CO)14(P(Mepy)Ph2) (4)
are described. In 1, 2 and 4 the phosphane ligand replaces the carbonyls and acts as a bridging bidentate P–N group. The formation
of 3 includes degradation of both the metal cluster core and the ligand itself. One of the P–C bonds in the ligand is cleaved and the
ligand caps a metal triangle with a bridging phosphido group together with the nitrogen donor. The reaction between dinuclear
Rh2(CO)4Cl2 and P(Mepy)Ph2 gives a binuclear Rh2(l-CO)Cl2(P(Mepy)Ph2)2 (5) with bridging ligands in a head-to-tail arrange-
ment. The crystal structure is also given.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Metal clusters; Phosphane; Pyridyl
1. Introduction
The monodentate coordination by phosphorus leaves
the N-donor available for further reactions. Chelation to
the same metal center is one possibility. This type of
coordination frequently leads to a strained, rather un-
stable four-membered ring system. Most typically, the
ligand forms binuclear complexes with between one and
three bridging ligands. PPh2py is a rigid ligand with a
short bite capacity. Because of its rigidity, the ligand
does not permit long distances between the bridged
metals. This makes PPh2py a convenient building block,
especially for binuclear complexes. The synthesis of bi-
nuclear homo- and heteronuclear compounds has been
studied widely in recent years [3]. The rich reactive
features of complexes with heterodonor ligands under
moderate conditions have attracted considerable atten-
tion because of their possible applications in catalyst
design [4].
Diphenyl(2-pyridyl)phosphane (PPh2py) (Scheme 1)
is a bidentate heterodonor ligand with a variable coor-
dination capability. The coordination types of the ligand
in mono- and dinuclear transition metal complexes have
been reviewed by Zhang and Cheng [1] and Newkome
[2].
In principle, the simple monodentate coordination of
PPh2py is possible via either phosphorus or nitrogen
atoms. Nitrogen is stronger r donor, but it is also a
weaker p-acceptor, which explains the preference for
coordination through the phosphorus. In fact, several
monodentate P-bonded complexes are known, while no
monodentate nitrogen-bonded compounds have been
reported thus far. In these cases, the reactions and the
bonding of the ligand closely resemble those of PPh3.
The heterodonor nature of the ligand also offers al-
ternative coordination modes in multinuclear com-
plexes. PPh2py has previously been found to be reactive
towards transition metal clusters. Its reactions with
* Corresponding author. Tel.: +358-13-251-3335; fax: +358-13-251-
3390.
€€
E-mail address: Sirpa.Jaaskelainen@Joensuu.fi (S. Jaaskelainen).
€
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.01.006

S. J€a€askel€ainen et al. / Journal of Organometallic Chemistry 689 (2004) 1064–1070
1065
P
P
N
N
Scheme 1. PPh2py and P(Mepy)Ph2.
Ru3(CO)12 are among the most studied processes [5],
and the derivatives of Os3(CO)12 [6,7], Os4(CO)12 [8],
Co4(CO)12 [9] and Ir4(CO)12 [10,11] are also reported.
Previously, we have studied several mixed-donor
(P/O, P/S, P/N), potentially bidentate triphenylphos-
phane derivatives. We have studied their synthesis and
their coordination modes in mono- and dinuclear rho-
dium complexes [12]. In addition, the dependence be-
tween the electronic and steric properties of the
phosphanes used as a cocatalyst in alkene hydroformy-
lation and in the chemo- and regioselectivity of the
products has been studied [13,14]. Furthermore, we have
systematically studied the reactions of the cluster family
HxRuxCoyRhz(CO)12 with various types of ligands,
such as phosphanes, thioethers, selenium and tellurium
compounds. In these studies, we found clear site selec-
tivities that depend on the metal composition and the
ligand [15–18].
Fig. 1. Molecular structure of HRuCo3(CO)10(P(Mepy)Ph2) (1). Se-
ꢀ
lected bond lengths (A) and angles (°): Co(2)–Ru(1) 2.7708(3), Co(3)–
Ru(1) 2.6142(3), Co(2)–Co(3) 2.4217(4), Co(1)–Ru(1) 2.6483(3),
Co(1)–Co(3) 2.5135(4), Co(1)–Co(2) 2.5012(4), N(1)–Co(3) 2.007(2),
P(1)–Co(2) 2.1832(6), N(1)–C(32)–P(1) 113.84(15), C(32)–P(1)–Co(2)
115.00(7), C(32)–N(1)–Co(3) 122.75(14).
In the present study, we investigated the coordination
modes of the methyl-substituted derivative of di-
phenyl(2-pyridyl)phosphane (PPh2py) (3-methyl-2-pyr-
idyl)diphenylphosphane (P(Mepy)Ph2) (Scheme 1), in
polynuclear metal clusters. The reactivity of
P(Mepy)Ph2 towards the tetranuclear homometallic
cluster Rh4(CO)12 and, for the sake of comparison, also
in the dinuclear complex Rh2(CO)4Cl2 was subjected to
examination. In particular, we were interested in reac-
tions involving the mixed metal compounds
HRuCo3(CO)12 and HRuRh3(CO)12.
the other carbonyls are terminal. The site selectivity of
carbonyl substitution in HRuCo3(CO)12 has been re-
ported earlier [18]. In disubstituted derivatives, ligands
such as phosphane or sulphur are typically bound to
cobalt atoms. If the reactions are conducted using
stronger donors such as TeMe2, coordination to apical
ruthenium becomes preferable. In addition, the forma-
tion of isomeric mixtures or the isomerization of the
compounds is also possible, depending on the nature of
the ligand.
The hydride ligand can be located on the Ru–Co(2)
edge in the crystal structure. Further support for the
hydride position is obtained for the Ru–Co bond
2. Results and discussion
ꢀ
lengths: the bridged bond is 2.7708(3) A while the non-
ꢀ
bridged bonds are 2.6483(3) and 2.6142(3) A. The
P(Mepy)Ph2 bonded Co–Co bond length is slightly
shorter 2.4217(4) than the other two bonds 2.5135(4)
2.1. Synthesis and structure of HRuCo3(CO)10
(P(Mepy)Ph2) (1)
ꢀ
and 2.5012(4) A.
When
a
tetrahedral mixed metal cluster
1
HRuCo3(CO)12 reacts with the P(Mepy)Ph2 ligand in
refluxing dichloromethane, HRuCo3(CO)10(P(Mepy)-
Ph2) (1) is formed as the only stable product. The crystal
structure (Fig. 1) shows that the P(Mepy)Ph2 ligand is
coordinated in the bridging mode to two adjacent cobalt
atoms by replacing two axial carbonyl ligands. Apart
from this, the cluster structure remains intact. The apical
ruthenium has three terminal carbonyl groups. The co-
balt triangle has a bridging carbonyl on each edge, and
In the H NMR of 1, signal at )20.6 ppm (d) with
2JH–P ¼ 18 Hz can be seen in the hydride region. The
parent cluster HRuCo3(CO)12, as well as most of its
phosphane or chalcogenide derivatives, has the hydride
ligand in the l3-Co3 position, which produces a broad
signal at )19.6 ppm. The coordination of the bulky
donor ligand makes the basal position less favoured in
the case of 1. One derivative known earlier, with a Ru–
Co edge-bridging hydride, is HRuCo3(CO)9[HC(PPh3)],

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S. J€a€askel€ainen et al. / Journal of Organometallic Chemistry 689 (2004) 1064–1070
which produces a resonance at )20.6 ppm with
2JH–P ¼ 27:5 Hz [19].
2.2. Synthesis and structures of HRuRh3(CO)10
(P(Mepy)Ph2) (2) and RuRh2(CO)9(P(Mepy)Ph)
(3)
The P(Mepy)Ph2 ligands also readily react with
HRuRh3(CO)12. With short reaction times (ca. 30 min),
the primary product is HRuRh3(CO)10(P(Mepy)Ph2) (2)
(Fig. 2). As in the case of the RuCo3 cluster, the ligand
assumes a bridging coordination mode, and it replaces
the carbonyl groups in two adjacent rhodiums, while the
rest of the cluster remains intact.
In the parent cluster HRuRh3(CO)12, the hydride li-
gand is fluxional in solution. It can exist in the basal
1
rhodium plane in the l3-position, which in H NMR
yields a quartet at )15.6 ppm (1JH–Rh ¼ 11 Hz) or
equally in one of the Ru–Rh bonds, yielding a doublet at
)18.5 ppm. (1JH–Rh ¼ 16 Hz) [20].
Fig. 3. Molecular structure of RuRh2(CO)9(P(Mepy)Ph) (3). Selected
ꢀ
In the crystal structure of the P(Mepy)Ph2 derivative
2, the hydride can be located in the Ru–Rh(2) bond.
Again, the hydride causes lengthening of the metal
bond lengths (A) and angles (°): Ru(1)–Rh(1) 2.8262(10), Ru(1)–Rh(2)
2.8757(10), Rh(1)–Rh(2) 2.7761(10), P(1)–Rh(1) 2.300(2), P(1)–Ru(1)
2.317(2), N(1)–Rh(2) 2.208(8), N(1)–C(32)–P(1) 109.4(6), C(32)–P(1)–
Ru(1) 117.9(3), C(32)–P(1)–Rh(1) 115.8(3), C(32)–N(1)–Rh(2)
121.6(6).
ꢀ
bond: the bridged Ru–Rh bond is 2.8829(4) A, while the
ꢀ
non-bridged bonds are 2.6791(4) and 2.7383(4) A. The
1H NMR shows a doublet of doublets at )17.2 ppm
(1JH–Rh ¼ 60 Hz, 2JH–P ¼ 20 Hz). In the 31P–{1H} NMR
Fig. 4. Molecular structure of Rh6(CO)14(P(Mepy)Ph2) (4). Selected
ꢀ
bond lengths (A) and angles (°): Rh(1)–Rh(2) 2.6703(4), Rh(1)–Rh(5)
Fig. 2. Molecular structure of HRuRh3(CO)10(P(Mepy)Ph2) (2). Se-
ꢀ
2.7695(4), Rh(1)–Rh(4) 2.7755(4), Rh(1)–Rh(6) 2.7765(4), Rh(2)–
Rh(6) 2.7192(4), Rh(2)–Rh(4) 2.7244(4), Rh(2)–Rh(3) 2.7372(4),
Rh(3)–Rh(4) 2.7432(4), Rh(3)–Rh(6) 2.7757(4), Rh(3)–Rh(5)
2.7820(4), Rh(4)–Rh(5) 2.7721(4), Rh(5)–Rh(6) 2.7367(4), N(1)–Rh(2)
2.185(3), P(1)–Rh(1) 2.2894(9), N(1)–C(32)–P(1) 116.5(3), C(32)–P(1)–
Rh(1) 113.82(11), C(32)–N(1)–Rh(2) 126.8(2).
lected bond lengths (A) and angles (°): Ru(1)–Rh(3) 2.6791(4), Ru(1)–
Rh(1) 2.7383(4), Ru(1)–Rh(2) 2.8829(4), Rh(1)–Rh(2) 2.7603(3),
Rh(1)–Rh(3) 2.7673(3), Rh(2)–Rh(3) 2.6375(3), N(1)–Rh(3) 2.208(3),
P(1)–Rh(2) 2.2789(9), N(1)–C(32)–P(1) 115.8(2), C(32)–P(1)–Rh(2)
116.12(10), C(32)–N(1)–Rh(3) 125.0(2).

S. J€a€askel€ainen et al. / Journal of Organometallic Chemistry 689 (2004) 1064–1070
1067
spectrum a doublet at 3.7 ppm, with P–Rh coupling
constants of 129 Hz is present. The Rh–Rh bond length
of the P(Mepy)Ph2 bridged bond is slightly shorter
2.6375(3) than the two other bonds 2.7603(3) and
2.7673(3).
phosphane ligand as the main product. The formation
of Rh6 derivatives from the reactions of Rh4 is a typical
cluster rearrangement. Rh6(CO)16 cluster has two ter-
minal carbonyls at every metal and four triply bridging
carbonyls at opposite sides of the metal octahedron. The
structure of 4 is a Rh6(CO)16 derivative, where two
terminal carbonyls at adjacent metals are replaced by a
When the reaction time between the HRuRh3(CO)12
and the P(Mepy)Ph2 was lengthened (approx. 2 h), a
new trinuclear mixed-metal compound, RuRh2(CO)9-
(P(Mepy)Ph) (3), was obtained (Fig. 3). It seems likely
that 3 is formed when the bridging ligand in 2 stages
an attack on the cluster core. As a result, both the metal
core and the ligand structure are then ruptured. In 3
the phosphorus atom has created a bond with both
the ruthenium and rhodium at the same time, and one of
the phenyl rings is removed from the ligand. A similar
type of coordination in the Ru3 cluster has been de-
scribed previously. The oxidative cleavage of a P–C
bond in PPh2py provides an organic fragment, PPhpy,
which caps the metal triangle through the bridging
phosphido group together with the nitrogen of the
pyridyl ring. The addition opens one metal bond and
leads to the formation of an r-bonded arylgroup. In
many cases, the reductive elimination of benzene is
subsequently favored in the presence of the hydride
ligand [1,21,22].
31
bridging P(Mepy)Ph2. NMR shows a doublet at 24.3
ppm, 1JP–Rh ¼ 142 Hz. The ligand bridged metal bond is
2.6703(4), the other bonds lie in the range 2.7192(4)–
2.7820(4). In this structure, the effect in metal bond
lengths is not so remarkable than in smaller ones.
2.4. Synthesis and structure of Rh2(CO)Cl2 (P(Mepy)-
Ph2)2 (5)
Treatment of Rh2(CO)4Cl2 with the ligand in ratio
Rh:L ¼ 1:1 leads to the formation of Rh2(CO)Cl2-
(P(Mepy)Ph2)2 (5) in good yield. The structure is given
in Fig. 5. Two ligands bridge the dimeric Rh skeleton at
the trans position. The chloride bridges of the original
compound have been broken and, in their place, a car-
bonyl bridged metal–metal bond is formed. The two
remaining chlorides are terminal.
The bridging ligands are orientated to produce a
head-to-tail conformation. The Rh–Rh distance is
No indication of hydride ligands in 3 was obtained
1
using H NMR spectroscopy. The 31P NMR spectrum
2.5846 A, which is indicative of a metal–metal bond.
ꢀ
1
has a doublet at 110.9 ppm, JP–Rh ¼ 96 Hz.
Such an arrangement is typical of these dimeric com-
plexed ligands bridged by a bidentate heterodonor. The
corresponding structure of Rh2(CO)Cl2(PPh2py) has
been published and the geometry discussed in detail
[23,24]. The spectroscopic data is consistent with the
data supplied for the pyridylphosphane derivative
published previously. 31P d ¼ 47:2 ppm J ¼ 140 Hz
2.3. Synthesis
(P(Mepy)Ph2) (4)
and
structure
of
Rh6(CO)14
Rh6(CO)14(P(Mepy)Ph2) (4) (Fig. 4) was formed in
the reaction between tetranuclear Rh4(CO)12 and the
ꢀ
Fig. 5. Molecular structure of Rh2(CO)Cl2(P(Mepy)Ph2)2 (5). Selected bond lengths (A) and angles (°): Rh(1)–Rh(2) 2.5846(8), Cl(1)–Rh(1) 2.367(2),
Cl(2)–Rh(2) 2.354(2), P(1)–Rh(1) 2.223(2), N(2)–Rh(2) 2.125(6), P(2)–Rh(2) 2.226(2), N(1)–Rh(1) 2.125(6), C(37)–Rh(1) 1.946(7), C(37)–Rh(2)
1.940(7), N(1)–C(18)–P(2) 111.9(5), C(18)–P(2)–Rh(2) 115.6(2), C(18)–N(1)–Rh(1) 121.2(5), Rh(2)–C(37)–Rh(1) 83.4(3), O(37)–C(37)–Rh(1)
137.2(6), O(37)–C(37)–Rh(2) 139.4(6).

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S. J€a€askel€ainen et al. / Journal of Organometallic Chemistry 689 (2004) 1064–1070
(44.18 ppm and 144.0 Hz for the pyridylphosphane
derivative) and IR CO stretching to 1797 cmꢀ1 is the
same for both compounds. Thus the methyl substituent
at the pyridyl ring has no noticeable effect on its reac-
tions.
3.3. Synthesis of 3 and 2
The HRuRh3(CO)12 (130 mg, 0.17 mmol) and
P(Mepy)Ph2 (60 mg, 0.23 mmol) were refluxed in H2Cl2
for 2 h. The solution was evaporated to dryness and
separated on silica column. The hexane–CH2Cl2 3:1
mixture gave the trinuclear 3 as an orange band. Yield
20 mg, 15%. Orange crystals of the product were ob-
tained from the CH2Cl2. IR(CH2Cl2): 2076vs, 2038s,
2023 vs, 2006m, 1993w, 1966w, 1886w, 1813w. NMR:
31P–{1H}: d ¼ 110:9 ppm, d, JP–Rh ¼ 96 Hz. The hex-
ane–CH2Cl2 2:1 mixture gave the tetranuclear 2 as an
orange band. Yield 22 mg, 13%. Red crystals of the
product were obtained from the CH2Cl2. IR(CH2Cl2):
2087w, 2073s, 2037s, 2024m, 2001vs, 1858m, 1830m.
3. Experimental
3.1. General considerations
The reactions and chromatographic separations were
performed in N2 using deoxygenated solvents.
P(Mepy)Ph2 [25], HRuCo3(CO)12 [26], HRuRh3(CO)12
[27], Rh4(CO)12 [28] and Rh2(CO)4Cl2 [29] were pre-
pared using published methods. The IR spectra were
recorded in dichloromethane on a Nicolet 20 SX spec-
trometer. The NMR spectra were measured in CDCl3
on a Bruker AM-250 spectrometer using SiMe4 (1H) or
85% H3PO4 (31P–{1H}) standard.
NMR: 31P–{1H}: d ¼ 3:7 ppm, d, JRh–P ¼ 129 Hz, H:
1
2
d ¼ ꢀ17:2 ppm, d of d, JHꢀRh ¼ 60 Hz, JH–P ¼ 20 Hz.
In shorter reactions (30 min) 2 was the main product in
a 31% yield.
3.4. Synthesis of 4
3.2. Synthesis of 1
Rh4(CO)12 (120 mg, 0.156 mmol) and P(Mepy)Ph2
(43 mg, 0.156 mmol) were refluxed in CH2Cl2 for 1 h:30
min. The solution was evaporated to dryness and sepa-
rated on a silica column in N2. Elution with 4:1 and 1:1
hexane–CH2Cl2 mixtures produced small fractions of
byproducts. The hexane–CH2Cl2 1:2 mixture gave the
product 4 as a brown band. Yield 76 mg, 57%. Dark
crystals of the product were obtained from the CH2Cl2
at )40 °C. IR(CH2Cl2): 2088m, 2056vs, 2026 m, 2002w,
1778w, 1755w. NMR: 31P–{1H}: d ¼ 24:3 ppm, d,
JP–Rh ¼ 142 Hz. Further elution with CH2Cl2 gave a
brown band of byproducts.
The HRuCo3(CO)12 (120 mg, 0.20 mmol) and
P(Mepy)Ph2 (55 mg, 0.20 mmol) were refluxed in
CH2Cl2 for 1 h:45 min. The solution was evaporated to
dryness and separated on a silica column. Elution with
hexane and 2:1 hexane–CH2Cl2 produced fractions of
byproducts. The hexane–CH2Cl2 1:1 mixture gave
product 1 as a brown band. Yield 57 mg, 35%. Dark
cubic crystals of the product were obtained from the
CH2Cl2. IR(CH2Cl2): 2075s, 2006vs, 1972w, 1833m,
1
1811m. NMR: 31P–{1H}: d ¼ 35:7 ppm. H: d ¼ ꢀ20:6
2
ppm, d, JH–P ¼ 18 Hz.
Table 1
Crystal data for compounds 1–5
1
2
3
4 ꢁ 2CH2Cl2
5 ꢁ CH2Cl2
C34H20Cl4NO14PRh6 C38H34Cl4N2OP2Rh2
Empirical formula
Formula weight
Temperature (K)
C28H17Co3NO10PRu C28H17NO10PRh3Ru C21H11NO9PRh2Ru
968.20
836.26
150(2)
759.17
293(2)
1456.74
150(2) K
0.71073
Monoclinic
P21=c
944.23
293(2)
120(2) K
0.71073
Monoclinic
P21=n
ꢀ
k (A)
Crystal system
0.71073
Monoclinic
P21=n
0.71073
Monoclinic
P21=c
0.71073
Monoclinic
P21=c
Space group
ꢀ
a (A)
12.1310(2)
11.0890(2)
22.8930(2)
104.243(1)
2984.91(8)
4
12.4864(1)
11.1883(1)
23.2385(3)
105.004(1)
3135.78(6)
4
9.2012(4)
15.6249(7)
16.6607(7)
98.175(2)
2370.9(2)
4
11.4466(1)
26.5032(5)
15.0688(3)
111.473(1)
4254.14(12)
4
14.5912(3)
14.0388(3)
18.1459(2)
90.341(1)
3716.99(12)
4
ꢀ
b (A)
ꢀ
c (A)
b (°)
V (A )
3
ꢀ
Z
qcalc (Mg/m3)
1.861
2.246
2.051
2.130
2.127
2.124
2.274
2.627
1.687
1.296
l(Mo Ka) (mmꢀ1
)
a
R1 (I P 2r)
0.0249
0.0597
0.0244
0.0566
0.0515
0.1133
0.0264
0.0586
0.0630
0.1544
b
wR2 (I P 2r)
P
P
a R1 ¼ jjFoj ꢀ jFcjj= jFoj.
P
P
2
2 1=2
b wR2 ¼ ½ ½wðFo2 ꢀ Fc2Þ ꢂ= ½wðFo2Þ ꢂꢂ
.

S. J€a€askel€ainen et al. / Journal of Organometallic Chemistry 689 (2004) 1064–1070
1069
3.5. Synthesis of 5
5. Supplementary material
Rh2(CO)4Cl2 (50 mg, 0.13 mmol) and P(Mepy)Ph2
(73 mg, 0.26 mmol) were dissolved in methanol in sep-
arate flasks. The solutions were combined, and the
product 5 was formed as a brown solid. The product was
filtered from the solution, washed with methanol and
dried in a vacuum. Yield 80 mg, 72%. Orange crystals
were formed in the crystallization from the CH2Cl2.
IR(CH2Cl2): 1797 cmꢀ1. NMR: 31P–{1H}: d ¼ 47:2
ppm, d, JP–Rh ¼ 140 Hz.
The crystallographic data for compound 1 have been
deposited with the Cambridge Crystallographic Data
Centre as supplementary publication no. CCDC
219003–219007. Copies of this information may be ob-
tained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK [Fax: +44-(0)1223-
336033, E-mail: deposit@ccdc.cam.ac.uk].
References
3.6. X-ray structure determinations
[1] Z.-Z. Zhang, H. Cheng, Coord. Chem. Rev. 147 (1996) 1.
[2] G.R. Newkome, Chem. Rev. 93 (1993) 2067.
[3] G. Zhang, J. Zhao, G. Raudaschl-Sieber, E. Herdtweck, F.E.
The X-ray diffraction data were collected by means of
a Nonius KappaCCD diffractometer using Mo Ka ra-
diation (k ¼ 0:71073 A). The Denzo-Scalepack [30]
€
Kuhn, Polyhedron 21 (2002) 1737, and references therein.
ꢀ
[4] (a) E. Drent, P.H.M. Budzelaar, W.W. Jager, J. Stapersma, EP
441447 jne. Drent,E, EP 441446, GB 2240545, EP jne;
program package was used for cell refinements and data
reduction. All of the structures were solved by direct
methods using the SIR-97 (1) or SHELXS-97 (2–5) pro-
gram and the WinGX graphical user interface [31–33]. A
multiscan absorption correction based on equivalent
reflections (XPREP in SHELXTL v. 6.12) [34] was ap-
plied to 2 and 4 (the Tmin/Tmax values were 0.29531/
0.32936 and 0.22659/0.30332 for 2 and 4, respectively).
Other data were scaled by Denzo-Scalepack. Structural
refinements were performed using SHELXL-97 [35]. In
structures 1 and 2, the hydride hydrogens were located
from the difference Fourier map and refined isotropi-
cally. All of the other hydrogens were placed in idealized
positions and they were constrained to ride on their
parent atom. The crystallographic data are summarized
in Table 1. Selected bond lengths and angles are shown
in Figs. 1–5.
€
(b) H.K. Reinius, P. Suomalainen, H. Riihimaki, J. Pursiainen,
A.O.I. Krause, J. Catal. 199 (2001) 302.
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4. Summary
€€
€
[12] P. Suomalainen, S. Jaaskelainen, M. Haukka, R.H. Laitinen, J.T.
Pursiainen, T.A. Pakkanen, Eur. J. Inorg. Chem. (2000) 2607.
P(Mepy)Ph2 is a ligand that has variable coordina-
tion modes. Both phosphorus and nitrogen can be uti-
lized in coordination. In reactions with a metal cluster,
a simple substitution of the carbonyl groups is possi-
ble, but in some cases both the ligand and the clus-
ter may be ruptured, and the product is an adduct of
these fragments. The bridging ligand stabilizes the
metal cores. The site selectivity in the Ru–Co cluster
favors coordination of the ligand with the cobalt atoms.
In the mixed Ru–Rh cluster the coordination first occurs
with the rhodium atoms, but in the case of further re-
actions ruthenium may also be involved. Compared to
PPh2py, the additional methyl group in P(Mepy)Ph2
produces no essential difference in reactivity as a ligand.
The rich chemistry P–N ligands open up new opportu-
nities for modifying the catalytic properties of metal
clusters.
€
[13] P. Suomalainen, H.K. Reinius, H. Riihimaki, R.H. Laitinen, S.
Jaaskelainen, M. Haukka, J.T. Pursiainen, T.A. Pakkanen, A.O.I.
€€
€
Krause, J. Mol. Catal. A 169 (2001) 67.
€€
€
[14] P. Suomalainen, R. Laitinen, S. Jaaskelainen, M. Haukka, J.T.
Pursiainen, T.A. Pakkanen, J. Mol. Catal. A 179 (2002) 93.
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met. Chem. 391 (1990) 403.
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(1990) 81.
€€
€
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T.A. Pakkanen, J. Pursiainen, L. Toupet, D. Grandjean, Organo-
metallics 13 (1994) 2472.
ꢁ
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Determination, University of Gottingen, Germany, 1997.
[32] A. Altomare, M.C. Burla, M. Camalli, G.L. Cascarano, C.
Giacovazzo, A. Guagliardi, A.G.G. Moliterni, G. Polidori, R.
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[34] G.M. Sheldrick, SHELXTL, Version6.12, Bruker Analytical X-ray
Systems, Bruker AXS, Inc., Madison, WI, 2001.
[35] G.M. Sheldrick, SHELXL-97, Program for Crystal Structure
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€ €
Refinement, University of Gottingen, Gottingen, Germany,
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