Reactivity of [Ru2(CO)6(μ-PFu2)(μ- η1,η2-Fu)] (Fu = 2-furyl) towards diphosphanes - Substitution, polymerisation, cyclometallation and elimination reactions

Article abstract of DOI:10.1002/1099-0682(200208)2002:8<2103::AID-EJIC2103>3.0.CO;2-G

Thermal reaction of [Ru₂(CO)₆(μ-PFu₂)(μ- η¹,η²-Fu)] (Fu = 2-furyl) (1) with bis(diphenylphosphanyl)methane (dppm), bis(diphenylphosphanyl)amine (dppam), or bis(diphenylphosphanyl)methylamine (dppma),

Full text of DOI:10.1002/1099-0682(200208)2002:8<2103::AID-EJIC2103>3.0.CO;2-G

FULL PAPER
Reactivity of [Ru2(CO)6(µ-PFu2)(µ-η1,η2-Fu)] (Fu ؍ 2-furyl) towards
Diphosphanes ؊ Substitution, Polymerisation, Cyclometallation and
Elimination Reactions
Wai-Yeung Wong,*[a] Fai-Lung Ting,[a] and Wai-Lim Lam[a]
Keywords: Ruthenium / Phosphane ligands / Phosphido complexes
Thermal reaction of [Ru2(CO)6(µ-PFu2)(µ-η1,η2-Fu)] (Fu = 2-
furyl) (1) with bis(diphenylphosphanyl)methane (dppm),
bis(diphenylphosphanyl)amine (dppam), or bis(diphenylpho-
phane ligand. Interestingly, elimination of the coordinated
furyl moiety occurs during the formation of 5 and 6. Upon
reaction with bis(diphenylphosphanyl)butane (dppb), bis(di-
sphanyl)methylamine (dppma), produces the substitution phenylphosphanyl)pentane (dpppe), or bis(diphenylphos-
products [Ru2(CO)4(µ-PFu2)(µ-η1,η2-Fu)(µ-L)] [2 (L = dppm),
3 (L = dppam), 4 (L = dppma)] in good yields. The Ru−Ru
phanyl)ferrocene (dppf), cyclometallation is not favoured in
each case. Instead, [{Ru2(CO)5(µ-PFu2)(µ-η1,η2-Fu)}2(L)] [7a
edge is bridged by the diphosphane in each case, while the (L = dppb), 8a (L = dpppe), 9a (L = dppf)] and polymeric
µ-η1,η2-bound furyl fragment remains intact. When the reac- [Ru2(CO)4(µ-PFu2)(µ-η1,η2-Fu)(L)]n [7b (L = dppb), 8b (L =
tions were carried out using bis(diphenylphosphanyl)ethane
dpppe), 9b (L = dppf)] were obtained with the product yield
(dppe) or bis(diphenylphosphanyl)propane (dppp), the com- depending on the stoichiometry of the reactants. All these
pounds [Ru2(CO)5(µ-PFu2)(µ-η1-C6H4PPh(CH2)nPPh2)] [5 (n =
2), 6 (n = 3)] were isolated as the thermodynamic products in
which both P atoms chelate to one Ru centre to afford five-
(for 5) and six-membered (for 6) ruthenacycles, accompanied
by orthometallation of one of the phenyl rings of the phos-
new diruthenium complexes are electron-precise with 34
cluster valence electrons.
( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
2002)
Introduction
characterisation of a range of novel carbonyl(µ-phosphido)-
diruthenium complexes. These products are formed by dif-
ferent reaction pathways embracing (i) simple phosphane
substitution with displacement of carbonyl ligands, (ii)
polymerization, and (iii) phosphane coordination accom-
panied by cyclometallation. Another noteworthy feature of
these phosphane-containing compounds is the various
modes of coordination towards metal atoms which the li-
gands exhibit[15Ϫ18]. Three binding modes have been ob-
served for the diphosphanes used in our studies, namely
chelating, intrabridging, and interbridging (Scheme 1).
There is a continuing interest in the synthesis and chem-
istry of phosphido-bridged di- and polynuclear
complexes.[1Ϫ7] Several recent developments provide a
wealth of unexpected and intriguing reactivity of some di-
nuclear allenyl complexes of the type [M2(CO)6(µ-PPh2)(µ-
η1,η1α,β-Cα(R)ϭCβϭCR2)] (M ϭ Fe, Ru; R ϭ H, Ph) to-
wards mono- and bidentate phosphanes.[8Ϫ12] In these stud-
ies, the nature of the phosphane plays a significant role in
governing the reaction pathways involved and the final
products isolated.[8Ϫ12]
We are interested in the use of tris(2-furyl)phosphane
(PFu3) as a ligand in organometallic syntheses.[13,14] The
recent preparation of [Ru2(CO)6(µ-PFu2)(µ-η1,η2-Fu)] (1)
and its reactivity with 1-alkynes sparked our interest in the
synthesis of a new class of complexes with different ligand
environments.[13] In order to explore the synthetic potential
of this system, we have now initiated a comprehensive study
of the reactions of 1 with some diphosphane ligands.
Herein, we describe results on reactions of 1 with various
diphosphanes PPh2EPPh2 [E ϭ (CH2)n, n ϭ 1Ϫ5; N(H);
N(Me); or Fe(η5-C5H4)2], which lead to the formation and
[a]
Department of Chemistry, Hong Kong Baptist University,
Waterloo Road, Kowloon Tong, Hong Kong, P. R. China
E-mail: rwywong@hkbu.edu.hk
Scheme 1
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 1434Ϫ1948/02/0808Ϫ2103 $ 20.00ϩ.50/0
2103

W.-Y. Wong, F.-L. Ting, W.-L. Lam
FULL PAPER
In order to further investigate, how the separation be-
tween the P donor atoms in PPh2(CH2)nPPh2 (i.e. the value
of n) might affect the chemistry of such classes of com-
plexes, we have examined the reactions that take place with
the related bidentate phosphanes containing more methyl-
ene groups, namely bis(diphenylphosphanyl)ethane (dppe),
bis(diphenylphosphanyl)propane (dppp), bis(diphenylphos-
phanyl)butane (dppb), or bis(diphenylphosphanyl)pentane
(dpppe). To our surprise, two novel 34-electron phosphido-
stabilised diruthenium complexes [Ru2(CO)5(µ-PFu2)(µ-η1-
C6H4PPhCH2CH2PPh2)] (5) and [Ru2(CO)5(µ-PFu2)(µ-η1-
C6H4PPhCH2CH2CH2PPh2)] (6) were obtained as the ther-
modynamically stable products, upon reaction of 1 with
dppe or dppp at elevated temperatures. In both structures,
the two P atoms chelate to one Ru atom to result in five-
(for 5) and six-membered (for 6) ruthenacycles, followed by
orthometallation of one of the phenyl rings of
PPh2(CH2)nPPh2 (n ϭ 2, 3).[18] No sign of the formation of
polymeric species in these reactions was observed under our
experimental conditions. The transformation of these two
products is illustrated in Scheme 2. Most interestingly, in
marked contrast with 2Ϫ4, the µ-η1,η2-bonded furyl group
was found to be detached during the formation of 5 and 6
so as to stabilize the products to retain 34 cluster valence
electrons (CVE). However, the mechanism for this reaction
is not yet ascertained. The IR spectral features of 5 and 6
Results and Discussion
Synthesis and Spectroscopic Characterisation
Complex 1 reacts with an equimolar amount of the bi-
dentate phosphane, namely bis(diphenylphosphanyl)me-
thane (dppm), bis(diphenylphosphanyl)amine (dppam), or
bis(diphenylphosphanyl)methylamine (dppma), in refluxing
toluene to afford three new diruthenium compounds
[Ru2(CO)4(µ-PFu2)(µ-η1,η2-Fu)(µ-dppm)] (2), [Ru2(CO)4-
(µ-PFu2)(µ-η1,η2-Fu)(µ-dppam)] (3), and [Ru2(CO)4(µ-
PFu2)(µ-η1,η2-Fu)(µ-dppma)] (4) as the sole products after
TLC purification on silica, all in reasonable yield
(Scheme 2). They were isolated as bright yellow crystalline
solids and are soluble in common organic solvents. These
compounds display almost identical IR ν(CO) absorption
patterns, suggesting a great resemblance of their structures.
Each of the 31P{1H} NMR spectra of 2 and 4 consists of
two separated sets of resonance signals. The resonance due
to the phosphido-P atom shows equal coupling to the two
coincidentally equivalent P atoms of the chelating diphos-
phanes, thus appearing as a pseudo-triplet (2JPϪP ϭ 172 for
2 and 169 Hz for 4). For 3, a doublet of doublets appears
around δ ϭ 94.0 ppm, attributable to the µ-PFu2 entity and
two interpenetrating sets of doublets in close proximity
centred at δ ϭ 87.16 and 87.18 ppm were also observed for
the coordinated dppam ligand.
Scheme 2. (i) PPh2EPPh2; (ii) PPh2(CH2)nPPh2; (iii) dppf
2104
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111

Reactivity of [Ru2(CO)6(µ-PFu2)(µ-η1,η2-Fu)] (Fu ϭ 2-furyl) towards Diphosphanes
FULL PAPER
are almost identical, indicative that they have similar struc- organic solvents. By virtue of symmetry, they both present
tures. They exhibit different patterns from the dppm ana- almost equivalent 31P{1H} NMR spectra and each shows
logue. Their ν(CO) bands absorb at lower energies than two 31P resonances at δ ഠ 34.0 and 39.0 ppm. However, no
those of 1, in agreement with chelation of the strongly elec- attempts have been made to fully assign these signals. The
tron-donating phosphane ligands. They display three dis- rather upfield resonances observed for the µ-phosphido
tinct sets of resonances in the 31P{1H} NMR spectra and atom in 7 and 8 were found to be in line with that for the
afford a typical AMX spectrum in each case. Compound 5 disubstituted product [Ru2(CO)4(PFu3)2(µ-PFu2)(µ-η1,η2-
gives a characteristic doublet of doublets at δ ϭ 99.08 ppm Fu)] which gave a pseudo AX231P{1H} spectrum with a
(2JPϪP ϭ 25 and 146 Hz) due to the µ-PFu2 group and an- triplet at δ ϭ 48.00 ppm and a doublet at δ ϭ Ϫ12.28 ppm
other doublet of doublets at δ ϭ 68.36 ppm (2JPϪP ϭ 25 (2JPϪP ϭ 23 Hz) for the µ-PFu2 and PFu3 groups, respect-
and 146 Hz) for the orthometallated PPh moiety. We note ively, in an intensity ratio of 1:2.[23]
that the resonance peak at δ ϭ 65.67 ppm due to the PPh2
Attempts have also been made to study the interaction
group shows equal coupling to the other two cis-phos- between 1 and the organometallic diphosphane ligand
phorus atoms (2JPϪP ϭ 25 Hz), thereby appearing as a vir- [Fe(η5-C5H4PPh2)2] (dppf) in view of the considerable re-
tual triplet. A similar coupling phenomenon has been ob- search attention on the use of the latter in the syntheses
served in [CpW2(CO)5(µ-PPh2)(η2-dppe)].[19] The 31P{1H} of di- or polymetallic complexes.[24] Instead of producing a
NMR spectrum of 6 reveals three sets of doublets of doub- chelating complex as in 2Ϫ4, thermal reaction of 1 with
lets at δ ϭ 84.27, 21.82, and 20.60 ppm with the most dppf in a 2:1 molar ratio for a short period of time (ca. 1 h)
downfield signal corresponding to the phosphido group.
afforded the complex [{Ru2(CO)5(µ-PFu2)(µ-η1,η2-
As a continuation of our effort in the study of the effect Fu)}2(dppf)] (9a) in fairly good yield in which two phos-
of the methylene chain length on the identity of products phido-bridged diruthenium fragments are linked by a
formed, similar reactions with dppb or dpppe were also car- bridging
bis(diphenylphosphanyl)ferrocene
moiety
ried out and in none of the cases was the product analogous (Scheme 2). The two PPh2 groups in dppf are separated by
to other PPh2(CH)nPPh2-bridged species (n ϭ 1Ϫ3) ob- a large ferrocenyl moiety and are free to form bidentate
tained. Complex 1 undergoes a rapid ligand substitution complex 9a. On the contrary, the relatively short bridging
reaction with a 0.5 equiv. of dppb or dpppe in refluxing length between both PPh2 groups in PPh2EPPh2 [E ϭ CH2,
toluene for 1 h to give [{Ru2(CO)5(µ-PFu2)(µ-η1,η2- N(H), N(Me)] appears to hinder the adoption of such an
Fu)}2(dppb)] (7a) (70%) and [{Ru2(CO)5(µ-PFu2)(µ-η1,η2- interbridging mode. Spectroscopic and MS data of 9a are
Fu)}2(dpppe)] (8a) (65%) as yellow solids (Scheme 2). Their consistent with the formula of the product having a 2:1 stoi-
structures were firmly supported by spectroscopic data. chiometry (Ru2/dppf) with the loss of two CO ligands. The
There is also no indication of the formation of dppb- or IR spectrum of 9a shows a rather different ν(CO) pattern
dpppe-bridged analogues of 2Ϫ4. Apparently, the long from those of 2Ϫ4, indicating that an intrabridging interac-
methylene bridge separating two bulky PPh2 groups would tion probably did not happen in this case. Like the spectrum
favour the isolation of 7a and 8a. Although it is commonly of [{CpW2(CO)6(µ-PPh2)}2(dppf)],[19] two phosphorus
found that the dppe and dppp can form stable five- and doublets were clearly shown in its 31P{1H} NMR spectrum,
six-membered chelating rings with the metal centre without in agreement with the structure shown. An attempt to gen-
imposing strong steric interactions between the two PPh2 erate a polymeric complex was also carried out via the reac-
groups,[12,19Ϫ22] chelation at the Ru atom by the dppb or tion of 1 with dppf in a 1:1 stoichiometric ratio. Only a
dpppe is inhibited since the formation of 7- or 8-membered
rings is generally not feasible. Moreover, the formation of a
sterically unfavourable four-membered metallacycle for
dppm would disfavour coordination via a chelating mode.
When the experiment was conducted with an equimolar
amount of 1 and dppb or dpppe for 1 h, polymerisation
occurred producing yellow polymers [Ru2(CO)4(µ-PFu2)(µ-
η1,η2-Fu)(L)]n [7b (L ϭ dppb) or 8b (L ϭ dpppe)] in high
yields and purity, which could not be isolated by TLC or
column chromatography. Purification of the polymers was
accomplished by extraction of the yellow residues with sev-
eral portions of hot hexane, followed by repeated precipita-
tion from their toluene solutions with methanol. Both poly-
mers were characterized by Gel Permeation Chromato-
graphy (GPC) as low-molecular-weight substances. A pro-
longed heating of the reaction mixture was found to
increase the extent of polymerisation, and we observed that
polymer 7b shows 23 repeating units (Mw ϭ 24500, Mn ϭ
22700) in the main chain when the reaction is carried out
atoms and the labels on the phenyl rings are omitted; the labels on
for 10 h. They are both air-stable and soluble in common the carbonyl C atoms have the same labels as the O atoms
Figure 1. A perspective drawing of compound 2; for clarity, all H
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111
2105

W.-Y. Wong, F.-L. Ting, W.-L. Lam
FULL PAPER
trace quantity of 9a was detected in this reaction and its metrically bonded to Ru(1) and Ru(2). The furyl unit is σ-
yield was reduced as the time of reflux was increased. An bonded to Ru(2) and π-bonded to Ru(1). These compounds
air-stable polymeric substance [Ru2(CO)4(µ-PFu2)(µ-η1,η2- display only slight chelate ring twisting about the RuϪRu
Fu)(dppf)]n (9b) was obtained as the major product follow- axis for the diphosphane ligands and the torsion angles de-
ing similar purification procedures as for 7b and 8b. An fined by P(2)ϪRu(1)ϪRu(2)ϪP(3) are 7.3, 8.9, and 4.5° for
analytically pure sample of 9b was collected as an orange 2Ϫ4, respectively. Within the five-membered ruthenacycle
solid in 64% yield which is soluble in chlorinated solvents in 2, the structural parameters of the coordinated dppm are
such as CH2Cl2 and CHCl3. Analysis of 9b by GPC re- very similar to those found in other Ru2 complexes bridged
vealed a low-molecular-weight polymer (Mw ϭ 11400, by dppm, such as in [Ru2(CO)4(µ-PPh2){µ-η1,η2α,β-C(Ph)ϭ
˚
Mn ϭ 8550, average degree of polymerization ϭ 8). Com- CϭCPPh2}(µ-dppm)] [2.367(1)
A
and 113.6(2)°],[12]
pound 9b displays NMR spectroscopic data that is very [Ru2(CO)3(MeCN)(µ-O2CMe)(µ-dppm)2]ϩ [2.37(1) A and
˚
similar to that of the model complex 9a, except that its res- 113(2)°],[25]
and
[Ru2(CO)2(PPh3)(µ-PPh2)(µ1-η2-
[25]
CH2PPh2)(µ-dppm)]ϩ [2.405(3) A and 110.0(4)°].
The
˚
onance peaks are rather broad in appearance.
PϪNϪP angle for 3 is 126.0(4)°, in common with other
dinuclear compounds with bridging dppam in the literat-
ure.[26–31] The corresponding angle is 121.59(15)° for 4.
These angles are slightly larger than 118.9(2) and 114.6(1)°
in free dppam and dppma,[32] respectively. To date, rela-
tively few structural data are available for metal complexes
containing dppma as a bridging ligand.[32,33]
Crystal Structure Analyses
Perspective drawings of the structures of 2 (Figure 1,
Table 1), 3 (Figure 2, Table 1), 4 (Figure 3, Table 1), 5 (Fig-
ure 4, Table 2), 6 (Figure 5, Table 3), 8a (Figure 6, Table 4),
and 9a (Figure 7, Table 5) are shown together with the
atomic numbering schemes used and selected bond lengths
and angles are given. The general structural features of 2Ϫ4
The structural characterisations of 5 and 6 provide un-
are very similar. Each of them possesses a difurylphos- equivocal proof of the identity of both molecules in the
phido-bridged diruthenium skeleton and the RuϪRu edge solid state. Basically, both structures contain a difurylphos-
is spanned by a bridging PPh2EPPh2 {2 (E ϭ CH2), 3 [E ϭ phido-substituted diruthenium framework with the (CH2)n-
N(H)], 4 [E ϭ N(Me)]} ligand. In each case, the C- or bridged diphosphane ligands (n ϭ 2, 3) interacting with
N(R)-bridged (R ϭ H, Me) diphosphane forms a non- both metal atoms in an η1-bonding mode. The furyl moiety
planar, five-membered metallacyclic ring. While the RuϪRu that is originally present in 1 has been eliminated. The two
distances in 2Ϫ4 are relatively insensitive to the nature of P atoms chelate to Ru(1) to afford a sterically favourable
the bridging unit between both of the PPh2 end groups, five- and six-membered ruthenacycle for 5 and 6, respect-
they are shorter than those in 1 and other related dialkyne- ively, accompanied by orthometallation of one of the
bridged
Ru2
complexes
reported
recently
[ca. phenyl rings on the P(3) atom. The coordination around
2.7735(3)Ϫ2.8006(6) A].[13] For 2Ϫ4, the P(1) atom is asym- the Ru(1) and Ru(2) atoms is completed by two and three
˚
˚
Table 1. Selected bond lengths [A] and angles [°] for complexes 2, 3·0.5MeOH, and 4·2CH2Cl2
2
3·0·5MeOH
4·2CH2Cl2
Ru(1)ϪRu(2)
Ru(1)ϪP(1)
Ru(1)ϪP(2)
Ru(2)ϪP(1)
Ru(2)ϪP(3)
Ru(1)ϪC(13)
Ru(1)ϪC(14)
Ru(2)ϪC(13)
C(13)ϪC(14)
P(2)ϪX
2.7443(6)
2.325(2)
2.376(2)
2.299(2)
2.357(2)
2.363(6)
2.504(5)
2.093(6)
2.7292(11)
2.356(3)
2.348(2)
2.318(3)
2.327(3)
2.365(9)
2.501(9)
2.090(9)
1.388(12)
2.7339(4)
2.3370(9)
2.3728(9)
2.2951(9)
2.3416(9)
2.358(3)
2.558(3)
2.120(3)
1.390(10)
1.843(6) [X ϭ C(29)]
1.869(6) [X ϭ C(29)]
1.390(5)
1.717(3) [X ϭ N(1)]
1.717(3) [X ϭ N(1)]
1.682(7) [X ϭ N(1)]
1.704(7) [X ϭ N(1)]
P(3)ϪX
Ru(1)ϪP(1)ϪRu(2)
Ru(2)ϪRu(1)ϪP(1)
P(2)ϪRu(1)ϪRu(2)
P(3)ϪRu(2)ϪRu(1)
Ru(1)ϪC(14)ϪC(13)
Ru(1)ϪC(13)ϪRu(2)
Ru(2)ϪRu(1)ϪC(13)
Ru(2)ϪRu(1)ϪC(14)
Ru(1)ϪC(13)ϪC(14)
C(13)ϪRu(1)ϪC(14)
Ru(2)ϪC(13)ϪC(14)
P(2)ϪXϪP(3)
72.80(6)
53.16(5)
97.17(5)
91.45(4)
67.9(3)
75.76(19)
47.65(15)
75.61(13)
79.1(3)
33.0(2)
134.5(6)
71.46(7)
53.62(7)
94.55(7)
91.96(7)
68.1(5)
75.3(3)
47.8(2)
75.9(2)
78.9(6)
33.0(3)
134.6(7)
126.0(4) [X ϭ N(1)]
72.34(3)
53.12(2)
92.47(2)
93.79(2)
65.81(18)
75.05(10)
48.51(8)
75.31(8)
81.7(2)
32.54(11)
133.3(2)
121.59(15) [X ϭ N(1)]
114.3(4) [X ϭ C(29)]
2106
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111

Reactivity of [Ru2(CO)6(µ-PFu2)(µ-η1,η2-Fu)] (Fu ϭ 2-furyl) towards Diphosphanes
FULL PAPER
Figure 4. A perspective drawing of compound 5; for clarity, all H
atoms and the labels on the phenyl rings are omitted; the labels on
the carbonyl C atoms have the same labels as the O atoms
Figure 2. A perspective drawing of compound 3; for clarity, all H
atoms and the labels on the phenyl rings are omitted; the labels on
the carbonyl C atoms have the same labels as the O atoms
˚
Table 2. Selected bond lengths [A] and angles [°] for complex 5
Ru(1)ϪRu(2)
Ru(1)ϪP(2)
Ru(2)ϪP(1)
C(28)ϪC(33)
2.8786(3) Ru(1)ϪP(1)
2.3302(7) Ru(1)ϪP(3)
2.3189(8) Ru(2)ϪC(33)
1.409(5)
2.3410(7)
2.3488(7)
2.156(3)
Ru(1)ϪP(1)ϪRu(2)
Ru(2)ϪRu(1)ϪP(2)
76.30(2) Ru(2)ϪRu(1)ϪP(1) 51.50(2)
154.39(2) Ru(2)ϪRu(1)ϪP(3) 79.90(2)
Ru(1)ϪRu(2)ϪC(33) 92.74(8) Ru(1)ϪP(3)ϪC(28) 116.20(11)
Ru(2)ϪC(33)ϪC(28) 122.4(2) P(3)ϪC(28)ϪC(33) 116.7(2)
Figure 3. A perspective drawing of compound 4; for clarity, all H
atoms and the labels on the phenyl rings are omitted; the labels on
the carbonyl C atoms have the same labels as the O atoms
terminal carbonyl ligands, respectively. For 5, the dppe li-
gand was shown to coordinate to the Ru centres, being bon-
ded to Ru(1) through both P(2) and P(3) atoms, and to
Ru(2) through the C(33) atom of the orthometallated ring.
The torsion angle defined by P(2)ϪC(26)ϪC(27)ϪP(3) is
45.5°. A salient structural feature observed in the structure
of 6 is the formation of a six-membered ring, which adopts
a stable chair conformation. The P(2) and P(3) atoms are
bonded to Ru(1) within the metallacycle. The Ru(2)ϪC(40)
Figure 5. A perspective drawing of compound 6; for clarity, all H
atoms and the labels on the phenyl rings are omitted; the labels on
the carbonyl C atoms have the same labels as the O atoms
[12,13,34Ϫ36]
˚
distance [2.174(2) A] is typical of a RuϪC bond.
Both compounds have 34 CVE and the EAN rule supports
the metalϪmetal bond formation based on the three- and
five-electron contribution from the phosphido and at C(32). The CϪC bonds in the aliphatic pentamethylene
C6H4PPh(CH2)nPPh2 (n ϭ 2, 3) units, respectively.
chain of the molecule are staggered with CϪC bond lengths
˚
For 8a, the dpppe ligand links two identical [Ru2(CO)5(µ- between 1.509(6) and 1.511(6) A and CϪCϪC angles be-
PFu2)(µ-η1,η2-Fu)] units such that the two halves of the tween 111.4(5) and 115.4(6)°. Complex 9a reveals a sym-
molecule are symmetrically related by an inversion centre metrical dppf-bridged structure in which a dppf unit is
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111
2107

W.-Y. Wong, F.-L. Ting, W.-L. Lam
FULL PAPER
˚
Table 3. Selected bond lengths [A] and angles [°] for complex
6·0.5MeOH
Ru(1)ϪRu(2)
Ru(1)ϪP(2)
Ru(2)ϪP(1)
C(35)ϪC(40)
2.8597(3) Ru(1)ϪP(1)
2.3339(7) Ru(1)ϪP(3)
2.3263(7) Ru(2)ϪC(40)
1.402(3)
2.3442(6)
2.3650(6)
2.174(2)
Ru(1)ϪP(1)ϪRu(2)
75.51(2) Ru(2)ϪRu(1)ϪP(1) 51.961(17)
Ru(2)ϪRu(1)ϪP(2) 152.630(17) Ru(2)ϪRu(1)ϪP(3) 86.338(16)
Ru(1)ϪRu(2)ϪC(40) 92.06(6) Ru(1)ϪP(3)ϪC(35) 115.16(7)
Ru(2)ϪC(40)ϪC(35) 125.70(17) P(3)ϪC(35)ϪC(40) 120.31(17)
Figure 7. A perspective drawing of compound 9a; for clarity, all H
atoms and the labels on the phenyl rings are omitted; the labels on
the carbonyl C atoms have the same labels as the O atoms
˚
Table 5. Selected bond lengths [A] and angles [°] for complex
9a·CH2Cl2
Ru(1)ϪRu(2)
Ru(1)ϪP(1)
Ru(2)ϪP(2)
Ru(3)ϪP(4)
Ru(1)ϪC(19)
Ru(2)ϪC(20)
Ru(3)ϪC(65)
Ru(4)ϪC(65)
2.8200(6) Ru(3)ϪRu(4)
2.3264(17) Ru(2)ϪP(1)
2.3651(13) Ru(3)ϪP(3)
2.3671(14) Ru(4)ϪP(4)
2.7763(6)
2.3545(14)
2.3617(13)
2.3252(14)
2.378(5)
1.389(8)
2.419(5)
2.063(6)
2.419(5)
2.362(5)
2.068(6)
Ru(2)ϪC(19)
C(19)ϪC(20)
Ru(3)ϪC(66)
C(65)ϪC(66)
1.395(7)
Figure 6. A perspective drawing of compound 8a; for clarity, all H
atoms and the labels on the phenyl rings are omitted; the labels on
the carbonyl C atoms have the same labels as the O atoms
Ru(1)ϪP(1)ϪRu(2)
74.09(5) Ru(2)ϪRu(1)ϪP(1)
53.41(4)
Ru(1)ϪRu(2)ϪP(2) 151.81(4) Ru(1)ϪC(19)ϪC(20) 135.7(4)
Ru(2)ϪC(20)ϪC(19) 71.6(3) Ru(1)ϪC(19)ϪRu(2) 78.49(18)
Ru(1)ϪRu(2)ϪC(19) 45.78(13) Ru(1)ϪRu(2)ϪC(20) 75.05(13)
Ru(2)ϪC(19)ϪC(20) 74.8(3)
Ru(3)ϪP(4)ϪRu(4)
Ru(4)ϪRu(3)ϪP(3) 156.10(4) Ru(3)ϪC(66)ϪC(65) 70.8(3)
Ru(3)ϪC(65)ϪRu(4) 77.29(17) Ru(4)ϪRu(3)ϪC(65) 46.61(14)
Ru(4)ϪRu(3)ϪC(66) 75.91(13) Ru(3)ϪC(65)ϪC(66) 75.3(3)
C(65)ϪRu(3)ϪC(66) 33.91(18) Ru(4)ϪC(65)ϪC(66) 134.8(4)
C(19)ϪRu(2)ϪC(20) 33.65(18)
˚
Table 4. Selected bond lengths [A] and angles [°] for complex
72.55(4) Ru(4)ϪRu(3)ϪP(4)
53.03(4)
8a·CH2Cl2
Ru(1)ϪRu(2)
Ru(2)ϪP(1)
Ru(1)ϪC(14)
Ru(2)ϪC(14)
2.7934(5) Ru(1)ϪP(1)
2.3243(13) Ru(1)ϪP(2)
2.3592(12)
2.3511(11)
2.398(4)
2.347(4)
2.073(4)
Ru(1)ϪC(15)
C(14)ϪC(15)
1.401(6)
Ru(1)ϪP(1)ϪRu(2)
73.23(4) Ru(2)ϪRu(1)ϪP(1)
52.81(3)
Ru(2)ϪRu(1)ϪP(2) 150.19(3) Ru(1)ϪC(15)ϪC(14) 70.8(3)
Ru(1)ϪC(14)ϪRu(2) 78.12(15) Ru(2)ϪC(14)ϪC(15) 135.1(3)
Ru(2)ϪRu(1)ϪC(14) 46.56(11) Ru(2)ϪRu(1)ϪC(15) 76.28(10)
C(14)ϪRu(1)ϪC(15) 34.33(15)
Concluding Remarks
The work presented here concerns the reaction chemistry
of [Ru2(CO)6(µ-PFu2)(µ-η1,η2-Fu)] (Fu ϭ 2-furyl) (1) with
various bidentate phosphane ligands. The general reactivity
sandwiched by two µ-phosphido Ru2 moieties to afford a patterns comprise chemical transformations involving (i)
heterometallic complex aggregate. The average RuϪRu substitution of CO ligands by phosphanes via intrabridging
˚
bond length is 2.7982(6) A. The retention of the dissociated or interbridging coordination modes to afford discrete or
furyl fragment in the structure is highlighted by the forma- polymeric molecules, or (ii) cyclometallation reactions ac-
tion of a σ and a π bonds between the furyl fragment and companied by reductive elimination of the dissociated furyl
the Ru2 core at both ends, similar to those mentioned before moiety. In our studies, three bonding types have been enco-
in 2Ϫ4. The two PPh2 groups are oriented in an anti config- untered for the diphosphanes used: chelating, intrabridging,
uration and the two P atoms are displaced from each cyclo- and interbridging. We have also investigated in detail the
˚
pentadienyl ring (away from the Fe atom) by 0.2461 A for factors dictating the preference for a particular coordina-
˚
P(2) and Ϫ0.2649 A for P(3). The two phosphanylcyclopen- tion geometry and we observe that the mode of coordina-
tadienyl rings are nearly parallel (dihedral angles 4.4°), tion is dependent on the nature and the length of the link-
planar and deviate by 8.1° from the idealised eclipsed con- ing chains between the terminal PPh2 groups. Although the
formation.
dominant reaction pathway involves replacement of CO li-
2108
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111

Reactivity of [Ru2(CO)6(µ-PFu2)(µ-η1,η2-Fu)] (Fu ϭ 2-furyl) towards Diphosphanes
FULL PAPER
7.62 (m, 4 H, Ph), 7.71 (s, 1 H, Fu) ppm. 31P{1H} NMR (CDCl3):
gands by phosphido groups to give substitution products in
the majority of cases, thermolysis of 1 with dppe or dppp
results in orthometallation of the phenyl ring to yield ther-
modynamically stable 34-electron complexes containing a
µ-η1-C6H4PPh(CH2)nPPh2 (n ϭ 2, 3) moiety along with the
unprecedented detachment of the original furyl fragment
2
2
δ ϭ 87.16 (d, JPϪP ϭ 191 Hz, PPh2), 87.18 (d, JPϪP ϭ 162 Hz,
2
PPh2), 93.97 (dd, JPϪP ϭ 162, 191 Hz, PFu2) ppm. FAB MS:
m/z ϭ 876 [(M Ϫ 2 CO)ϩ]. C40H30NO7P3Ru2 (931.74): calcd. C
51.56, H 3.25, N 1.50; found C 51.30, H 3.16, N 1.32.
[Ru2(CO)4(µ-PFu2)(µ-η1,η2-Fu)(µ-dppma)] (4): This compound was
from precursor 1. Work is in progress to study the reactivity prepared similarly as described above for 2 and 3 from 1 (50 mg,
0.083 mmol) and dppma (33 mg, 0.083 mmol). The resulting red-
dish-orange mixture was subjected to preparative TLC eluting with
hexane/CH2Cl2 (3:1, v/v). From the bright yellow band (Rf ϭ 0.21),
the title compound was obtained in 42% yield (33 mg) as bright
yellow block-shaped crystals upon recrystallisation from hexane/
CH2Cl2 under ambient conditions. IR (CH2Cl2): ν˜ ϭ 2007 s, 1988
vs, 1944 vs [ν(CO)] cmϪ1. 1H NMR (CDCl3): δ ϭ 2.47 (t, 3JHϪP ϭ
6.4 Hz, 3 H, NMe), 5.02 (m, 1 H, Fu), 5.28 (m, 1 H, Fu), 6.34Ϫ6.38
(m, 3 H, Fu), 6.49 (m, 1 H, Fu), 6.68 (m, 1 H, Fu), 7.44 (m, 16 H,
Ph), 7.66 (s, 1 H, Fu), 7.72 (m, 4 H, Ph), 7.75 (s, 1 H, Fu) ppm.
of 1 with other organic and organometallic nucleophilic re-
agents.
Experimental Section
General Procedures: All reactions were conducted under dry nitro-
gen with the use of standard Schlenk techniques. Solvents for pre-
parative work were dried and distilled before use. Unless otherwise
stated all reagents were obtained from commercial suppliers and
used without further purification. The syntheses of complex 1[13]
and the ligands dppam[28,29] and dppma[32] were carried out as re-
ported previously. IR spectra were recorded as CH2Cl2 solutions
with a PerkinϪElmer Paragon 1000 PC or Nicolet Magna 550
Series II FTIR spectrometer. NMR spectra were measured in
CDCl3 with a JEOL EX270 or a Varian Inova 400 MHz FT NMR
spectrometer, with 1H NMR chemical shifts quoted relative to
SiMe4 and 31P chemical shifts relative to an 85% H3PO4 external
standard. Fast atom bombardment (FAB) mass spectra were re-
corded in m-nitrobenzyl alcohol matrices with a Finnigan-SSQ 710
spectrometer. Separation of products was accomplished by prepar-
ative TLC plates coated with silica (Merck, Kieselgel 60). The mo-
lecular weight of each polymer sample was estimated by GPC (HP
1050 series HPLC with visible wavelength and fluorescent de-
tectors) against polystyrene standards.
2
31P{1H} NMR (CDCl3): δ ϭ 91.80 (t, JPϪP ϭ 169 Hz, PFu2),
106.92 (d, 2JPϪP ϭ 169 Hz, PPh2) ppm. FAB MS: m/z ϭ 946 [Mϩ].
C41H32NO7P3Ru2 (945.77): calcd. C 52.07, H 3.41, N 1.48; found
C 51.73, H 3.25, N 1.70.
[Ru2(CO)5(µ-PFu2)(µ-η1-C6H4PPh(CH2)2PPh2)] (5): A mixture of
compound 1 (50 mg, 0.083 mmol) and dppe (33 mg, 0.083 mmol)
in toluene was stirred under reflux for 5 h resulting in a reddish-
brown mixture. Removal of the solvent followed by TLC separation
on silica eluting with hexane/CH2Cl2 (2:1, v/v) gave a yellow solid
of complex 5 (35 mg, 46%) after recrystallisation from a hexane/
CHCl3 mixture at room temperature. IR (CH2Cl2): ν˜ ϭ 2046 vs,
2002 vs, 1980 m, 1961 s [ν(CO)] cmϪ1 1H NMR (CDCl3): δ ϭ
.
1.98Ϫ2.06 (m, 2 H, CH2), 2.81Ϫ2.91 (m, 2 H, CH2), 5.45 (m, 1 H,
Fu), 5.91 (m, 1 H, Fu), 6.01 (m, 1 H, Fu), 6.19 (m, 1 H, Fu), 6.42
(t, 3JHϪH ϭ 7.6 Hz, 1 H, Fu), 6.70Ϫ7.63 (m, 19 H, aromatic), 8.06
3
(d, JHϪH ϭ 7.6 Hz, 1 H, Fu) ppm. 31P{1H} NMR (CDCl3): δ ϭ
[Ru2(CO)4(µ-PFu2)(µ-η1,η2-Fu)(µ-dppm)] (2): A solution of com-
plex 1 (50 mg, 0.083 mmol) in toluene (20 mL) was refluxed with
dppm (32 mg, 0.083 mmol) for 4 h. The solution gradually changed
from pale yellow to dark orange-yellow. The solvent was then re-
moved in vacuo and the residue taken up in CH2Cl2 for TLC sep-
aration eluting with hexane/CH2Cl2 (2:1, v/v). The bright yellow
band (Rf ϭ 0.34) consisting of 2 was obtained and the product was
isolated in 84% yield (65 mg). Recrystallisation of the product was
achieved by concentration of a hexane/CH2Cl2 solution at room
temperature, affording bright yellow block crystals. IR (CH2Cl2):
ν˜ ϭ 2007 s, 1985 vs, 1942 vs [ν(CO)] cmϪ1. 1H NMR (CDCl3): δ ϭ
2
2
65.67 (t, JPϪP ϭ 25 Hz, PPh), 68.36 (dd, JPϪP ϭ 25 and 146 Hz,
2
PPh), 99.08 (dd, JPϪP ϭ 25 and 146 Hz, PFu2) ppm. FAB MS:
m/z ϭ 850 [(M Ϫ 2 CO)ϩ]. C39H29O7P3Ru2 (904.72): calcd. C
51.78, H 3.23; found C 51.42, H 3.16.
[Ru2(CO)5(µ-PFu2)(µ-η1-C6H4PPh(CH2)3PPh2)] (6): In a manner
similar to compound 5, refluxing a toluene solution (20 mL) of 1
(50 mg, 0.083 mmol) and dppp (34 mg, 0.083 mmol) in a 1:1 molar
ratio for 5 h produced a dark yellowish-brown solution. The usual
workup procedures afforded a colourless TLC band (hexane/
CH2Cl2, 4:1, v/v; Rf ϭ 0.31), which became apparent under UV
light. The title complex was subsequently isolated as a pale yellow
solid in 40% yield (31 mg). IR (CH2Cl2): ν˜ ϭ 2049 vs, 2004 s, 1985
2
3.74 (t, JHϪP ϭ 10.8 Hz, 2 H, CH2), 4.87 (m, 1 H, Fu), 5.63 (m,
1 H, Fu), 6.33Ϫ6.46 (m, 4 H, Fu), 6.75 (s, 1 H, Fu), 7.27 (m, 16
s, 1959 s [ν(CO)] cmϪ1
.
1H NMR (CDCl3): δ ϭ 2.03Ϫ2.42 (m, 4
H, Ph), 7.54 (s, 1 H, Fu), 7.67 (m, 4 H, Ph), 7.74 (s, 1 H, Fu) ppm.
2
31P{1H} NMR (CDCl3): δ ϭ 41.61 (d, JPϪP ϭ 172 Hz, PPh2),
H, CH2), 2.85Ϫ3.06 (m, 2 H, CH2), 5.57 (m, 1 H, Fu), 5.96 (m, 1
3
100.46 (t, 2JPϪP ϭ 172 Hz, PFu2) ppm. FAB MS: m/z ϭ 931 [Mϩ].
C41H31O7P3Ru2 (930.75): calcd. C 52.91, H 3.36; found C 53.14,
H 3.30.
H, Fu), 6.10 (m, 1 H, Fu), 6.22 (m, 1 H, Fu), 6.56 (t, JHϪH
ϭ
7.6 Hz, 1 H, Fu), 6.74Ϫ7.91 (m, 19 H, aromatic), 8.22 (d, 3JHϪH ϭ
7.6 Hz, 1 H, Fu) ppm. 31P{1H} NMR (CDCl3): δ ϭ 20.60 (dd,
2JPϪP ϭ 31 and 38 Hz, PPh), 21.82 (dd, JPϪP ϭ 4 and 38 Hz,
2
[Ru2(CO)4(µ-PFu2)(µ-η1,η2-Fu)(µ-dppam)] (3): White powdered
dppam (32 mg, 0.083 mmol) was added to a toluene solution of 1
(50 mg, 0.083 mmol) and the mixture was stirred under reflux for
3 h to afford a bright yellow solution. The volatile materials were
removed in vacuo and subsequent workup by TLC purification
with hexane/CH2Cl2 (1:1, v/v) as eluent gave a yellow band (Rf ϭ
0.60) which furnished compound 3 as a yellow crystalline solid in
2
PPh), 84.27 (dd, JPϪP ϭ 4 and 31 Hz, PFu2) ppm. FAB MS:
m/z ϭ 919 [Mϩ]. C40H31O7P3Ru2 (918.74): calcd. C 52.29, H 3.40;
found C 52.01, H 3.19.
[{Ru2(CO)5(µ-PFu2)(µ-η1,η2-Fu)}2(dppb)] (7a) and [Ru2(CO)4(µ-
PFu2)(µ-η1,η2-Fu)(dppb)]n (7b): A toluene solution (20 mL) of 1
(50 mg, 0.083 mmol) was heated at reflux in the presence of a 0.5
44% (34 mg). IR (CH2Cl2): ν˜ ϭ 2011 s, 1989 vs, 1946 vs [ν(CO)] equiv. of dppb (18 mg, 0.042 mmol). After 1 h, the solvent was re-
1
cmϪ1. H NMR (CDCl3): δ ϭ 4.42 (m, 1 H, NH), 4.75 (m, 1 H, moved and the residue chromatographed. A yellow band, eluted
Fu), 5.92 (m, 1 H, Fu), 6.31Ϫ6.40 (m, 3 H, Fu), 6.73 (s, 1 H, Fu),
with hexane/CH2Cl2 (1:1, v/v), yielded the linking cluster 7a
7.17 (m, 1 H, Fu), 7.34 (m, 12 H, Ph), 7.48 (m, 5 H, Fu ϩ Ph), (46 mg, 70%) after recrystallisation from the same solvent mixture.
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111
2109

W.-Y. Wong, F.-L. Ting, W.-L. Lam
FULL PAPER
Mixing compound 1 with 1 mol-equiv. of dppb (0.083 mmol) in
toluene (20 mL), followed by heating to reflux for 1 h, generated a
deep yellow solution. TLC screening essentially revealed the ab-
sence of 7a. The solvent was removed and the crude solid obtained
7.20Ϫ7.46 (m, 26 H, Fu ϩ Ph), 7.54 (s, 2 H, Fu) ppm. 31P{1H}
NMR (CDCl3): δ ϭ 34.75 (m, PFu2 or PPh2), 49.15 (m, PFu2 or
PPh2) ppm. FAB MS: m/z ϭ 1561 [(M Ϫ CO)ϩ]. C63H48O16P4Ru4
(1589.24): calcd. C 47.61, H 3.04; found C 47.32, H 2.85. 8b: IR
after washing with hot hexane was redissolved in the minimum (CH2Cl2): ν˜ ϭ 2014 vs, 1981 m, 1951 s [ν(CO)] cmϪ1 1H NMR
.
volume of toluene. Analytically pure sample of 7b was isolated as a
(CDCl3): δ ϭ 2.08Ϫ2.67 (m, 8 H, CH2), 3.49 (m, 2 H, CH2), 4.88
yellow solid (56 mg, 69%) by repeated precipitation from methanol, (m, 1 H, Fu), 5.39 (m, 1 H, Fu), 6.12Ϫ6.34 (m, 4 H, Fu), 7.10Ϫ7.89
washing with hexane and drying in vacuo. 7a: IR (CH2Cl2): ν˜ ϭ
(m, 23 H, Fu ϩ Ph) ppm. 31P{1H} NMR (CDCl3): δ ϭ 34.22 (m,
2060 vs, 2006 vs, 1974 m, 1958 sh [ν(CO)] cmϪ1. 1H NMR (CDCl3): PFu2 or PPh2), 38.99 (m, PFu2 or PPh2) ppm. GPC (THF as elu-
δ ϭ 2.09Ϫ2.57 (m, 6 H, CH2), 3.50 (m, 2 H, CH2), 4.83 (m, 2 H, ent): Mw ϭ 8550, Mn ϭ 7270 (n ϭ 1.18). C45H39O7P3Ru2·0.5C6H14
Fu), 6.04Ϫ6.44 (m, 10 H, Fu), 7.08Ϫ7.57 (m, 26 H, Fu ϩ Ph) ppm.
31P{1H} NMR (CDCl3): δ ϭ 34.58 (m, PFu2 or PPh2), 48.80 (m,
PFu2 or PPh2) ppm. FAB MS: m/z ϭ 1491 [(M Ϫ 3 CO)ϩ].
C62H46O16P4Ru4 (1575.21): calcd. C 47.28, H 2.94; found C 46.95,
H 2.80. 7b: IR (CH2Cl2): ν˜ ϭ 2014 vs, 1982 m, 1951 s [ν(CO)]
(1029.95): calcd. C 55.98, H 4.50; found C 55.97, H 4.27.
[{Ru2(CO)5(µ-PFu2)(µ-η1,η2-Fu)}2(dppf)] (9a) and [Ru2(CO)4(µ-
PFu2)(µ-η1,η2-Fu)(dppf)]n (9b): Compound 1 (50 mg, 0.083 mmol)
and dppf (23 mg, 0.042 mmol) in a 2:1 molar ratio were dissolved
and mixed in toluene (20 mL). After heating to reflux and stirring
for about 1 h, the resulting mixture was purified by chromato-
graphy on silica plates using hexane/CH2Cl2 (3:1, v/v) as eluent,
leading to the isolation of an orange product 9a (Rf ϭ 0.38, 38 mg,
53%). When an equimolar amount of 1 and dppf (0.083 mmol) was
employed in the reaction whilst stirring for 1 h, an orange solution
resulted and the solvent was evaporated. The crude product was
then washed with several portions of hot hexane (3 ϫ 10 mL) and
the resulting solid was reprecipitated thrice from toluene/methanol
to produce an orange powder of 9b in 64% yield (59 mg) after dry-
1
cmϪ1. H NMR (CDCl3): δ ϭ 2.00Ϫ2.50 (m, 6 H, CH2), 3.49 (m,
2 H, CH2), 4.52 (m, 1 H, Fu), 5.36 (m, 1 H, Fu), 5.85Ϫ6.32 (m, 4
H, Fu), 7.05Ϫ7.56 (m, 23 H, Fu ϩ Ph) ppm. 31P{1H} NMR
(CDCl3): δ ϭ 34.33 (m, PFu2 or PPh2), 38.60 (m, PFu2 or PPh2)
ppm. GPC (THF as eluent): Mw ϭ 5030, Mn ϭ 4810 (n ϭ 1.05).
When the polymerization was performed for 10 h, Mw ϭ 24500,
Mn ϭ 22700 (n ϭ 1.08). C44H37O7P3Ru2·0.5C6H14 (1015.92): calcd.
C 55.57, H 4.37; found C 55.79, H 4.34.
[{Ru2(CO)5(µ-PFu2)(µ-η1,η2-Fu)}2(dpppe)] (8a) and [Ru2(CO)4(µ-
PFu2)(µ-η1,η2-Fu)(dpppe)]n (8b):
A
mixture of
0.083 mmol) and dpppe (19 mg, 0.042 mmol) in toluene (20 mL)
was heated to reflux for 1 h. Concentration of the resulting yellow (m, 2 H, C5H4), 4.32 (m, 2 H, C5H4), 4.52 (s, 2 H, Fu), 5.16 (s, 2
1
(50 mg, ing in vacuo. 9a: IR (CH2Cl2): ν˜ ϭ 2061 vs, 2005 vs, 1978 s, 1957
sh [ν(CO)] cmϪ1. 1H NMR (CDCl3): δ ϭ 3.78 (m, 4 H, C5H4), 4.05
solution followed by TLC separation gave a bright yellow band
(Rf ϭ 0.55) from which compound 8a was isolated in 65% yield
(43 mg). When a similar reaction was performed using a 1:1 molar
ratio of 1 and dpppe (0.083 mmol), the desired polymer 8b formed
after 1 h of reflux, which was worked up in a fashion identical to
H, Fu), 5.96 (s, 2 H, Fu), 6.18 (m, 4 H, Fu), 6.39 (m, 2 H, Fu),
6.97Ϫ7.51 (m, 24 H, Fu ϩ Ph), 7.66 (s, 2 H, Fu) ppm. 31P{1H}
NMR (CDCl3): δ ϭ 36.13 (d, 2JPϪP ϭ 20 Hz, PFu2 or PPh2), 47.86
2
(d, JPϪP ϭ 20 Hz, PFu2 or PPh2) ppm. FAB MS: m/z ϭ 1703
[Mϩ]. C68H46FeO16P4Ru4 (1703.13): calcd. C 47.96, H 2.72; found
that for 7b, to afford a yellow-orange solid (60 mg, 73%). 8a: IR C 47.52, H 2.40. 9b: IR (CH2Cl2): ν˜ ϭ 2014 vs, 1981 m, 1953 s
1
(CH2Cl2): ν˜ ϭ 2060 vs, 2006 vs, 1973 m, 1957 sh [ν(CO)] cmϪ1. 1H
[ν(CO)] cmϪ1. H NMR (CDCl3): δ ϭ 3.48Ϫ4.56 (m, br, 9 H, Fu
NMR (CDCl3): δ ϭ 2.25Ϫ2.62 (m, 8 H, CH2), 3.48 (m, 2 H, CH2), ϩ C5H4), 5.20 (m, 1 H, Fu), 5.81Ϫ6.02 (m, 3 H, Fu), 6.30 (m, 1
4.83 (s, 1 H, Fu), 4.90 (s, 1 H, Fu), 6.21Ϫ6.33 (m, 10 H, Fu),
H, Fu), 6.72Ϫ7.65 (m, 23 H, Fu ϩ Ph) ppm. 31P{1H} NMR
Table 6. Summary of crystal data
2
3·0.5H2O
4·2CH2Cl2
5
6·0.5MeOH
8a·CH2Cl2
9a·CH2Cl2
Empirical formula
C41H31O7-
P3Ru2
930.71
orthorhombic
Pna21
21.3556(15)
17.0951(12)
10.9896(8)
90
90
90
4012.0(5)
4
C40H30NO7-
P3Ru2·0.5H2O
940.71
monoclinic
P21/c
18.9075(14)
27.521(2)
15.1706(11)
90
90.1050(10)
90
C41H32NO7-
P3Ru2·2CH2Cl2
1115.58
triclinic
¯
P1
12.2529(13)
13.0394(14)
15.4098(16)
79.028(2)
71.699(2)
87.659(2)
2294.3(4)
2
C39H29O7-
P3Ru2
904.67
triclinic
¯
P1
9.6249(6)
11.2508(7)
18.0515(11)
105.9470(10)
91.0220(10)
95.0250(10)
1870.5(2)
2
C40H31O7-
P3Ru2·0.5MeOH
934.72
triclinic
¯
P1
10.1612(6)
11.5813(7)
18.8017(11)
78.5950(10)
80.1120(10)
67.5230(10)
1992.8(2)
2
C63H48O16
-
C68H46FeO16-
P4Ru2·CH2Cl2
1787.98
triclinic
¯
P1
11.5260(6)
16.4507(9)
19.0961(11)
81.0200(10)
75.8440(10)
85.0760(10)
3463.5(3)
2
P4Ru4·CH2Cl2
1674.17
monoclinic
I2/a
22.0907(14)
10.4004(7)
31.980(2)
90
98.4900(10)
90
7266.9(8)
4
Formula mass
Crystal system
Space group
˚
a [A]
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
7894.1(10)
8
Z
T [K]
F(000)
µ(Mo-Kα) [mmϪ1
293
1864
0.920
293
3768
0.938
293
1116
1.045
293
904
0.984
293
938
0.927
293
3328
1.037
293
1772
1.293
]
Reflections collected
Unique reflections
Rint
Observed reflections
GOF on F2
R1, wR2 [I Ͼ 2.0σ(I)][a]
19431
6147
0.0389
6147
0.998
38989
13841
0.0851
13841
0.908
0.0582, 0.1317
13482
9807
0.0179
9807
0.841
0.0364, 0.0993
11086
8062
0.0154
8062
0.779
0.0307, 0.0851
9946
6870
0.0174
6870
0.986
0.0355, 0.1095
17500
6364
0.0332
6364
1.031
20763
15005
0.0274
15005
0.876
0.0476, 0.1017
0.0395, 0.1035
0.0433, 0.1183
[a]
2
2
2 2 1/2
R1 ϭ Σ||Fo| Ϫ |Fc||/Σ|Fo|; wR2 ϭ [Σw(|Fo | Ϫ |Fc |)2/Σw|Fo | ]
.
2110
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111

Reactivity of [Ru2(CO)6(µ-PFu2)(µ-η1,η2-Fu)] (Fu ϭ 2-furyl) towards Diphosphanes
FULL PAPER
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X-ray Crystallography: Except for compounds 6 and 8a, good-qual-
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Received November 19, 2001
[I010466]
Eur. J. Inorg. Chem. 2002, 2103Ϫ2111
2111