Reactions of (Me2C)(Me2Si)[(η5-C 5H3)Mo(CO)3]2 with phosphanylalkynes: Rearrangement of phosphanylalkynes into phosphido-substituted vinylidenyl ligands by cleavage of the P-C(al

Article abstract of DOI:10.1002/ejic.200800704

This article deals with the thermal reactions of the doubly bridged bis(cyclopentadienyl) dinuclear molybdenum complex (Me₂C)(Me ₂Si)[(η⁵-C₅H₃)Mo(CO) ₃]₂ (1) with a series of pho

Full text of DOI:10.1002/ejic.200800704

FULL PAPER
DOI: 10.1002/ejic.200800704
Reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with Phosphanylalkynes:
Rearrangement of Phosphanylalkynes into Phosphido-Substituted Vinylidenyl
Ligands by Cleavage of the P–C(alkyne) Bond and Formation of a
P–C(alkene) Bond
Bin Li,[a] Shansheng Xu,[a] Haibin Song,[a] and Baiquan Wang*[a,b]
Keywords: Molybdenum / Phosphorus / Alkynes / Rearrangement / Bridging ligands / X-ray diffraction
This article deals with the thermal reactions of the doubly
bridged bis(cyclopentadienyl) dinuclear molybdenum com-
plex (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with a series of
phosphanylalkynes PhnP(CϵCR)3–n (n = 2, 1, 0; R = Ph, Fc).
In addition to the complex (Me2C)(Me2Si)[(η5-C5H3)2Mo2-
(CO)4(µ-η2-η2(Ќ)-R1CϵCR2)] [R1 = Ph, R2 = Ph2P, 2; R1 = Ph,
PhP(CϵCPh), 9] were also isolated when mono- and bis-
(ethynyl)-functionalized phosphanes reacted with 1. Reac-
tions of tris(ethynyl)-functionalized phosphanes with 1 af-
forded the phosphanylalkyne-bridged complexes (or/and
their oxide) (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(µ-η2-η2(Ќ)-
R1CϵCR2)] [R1 = Ph, R2 = P(CϵCPh)2, 11a and 11b; R1 = Ph,
R2 = P(O)(CϵCPh)2, 12; and R1 = Fc, R2 = P(CϵCFc)2, 13]. All
the new complexes were fully characterized. X-ray charac-
terization of 3, 5, 6, 7, 11a, 11b, 13, and P(CϵCFc)3 are also
provided.
R2 = Ph2P(O), 4; R1 = Ph, R2 = PhP(CϵCPh), 6; R1 = Fc, R2
=
PhP(CϵCFc), 8; and R1 = Fc, R2 = PhP(O)(CϵCFc), 10], in
which the phosphanylalkynes acted as disubstituted acetyl-
enes, the P–C(alkyne) bond cleavage and phosphanylalkyne
rearrangement products (Me2C)(Me2Si)[(η5-C5H3)2Mo2-
(CO)4{µ-η1-η2-C=C(R1)R2}] [R1 = Ph, R2 = Ph2P, 3; R1 = Fc, R2
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
= Ph2P, 5; R1 = Ph, R2 = PhP(CϵCPh), 7; and R1 = Fc, R2
=
unique properties in terms of structure, reactivity, and catal-
ysis in comparison to the properties exhibited by their non-
bridged and singly bridged analogues.[6] We recently re-
ported that the Me2C and Me2Si doubly bridged bis(cyclo-
pentadienyl) dinuclear molybdenum carbonyl complex
(Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) contained an un-
usually long Mo–Mo bond length,[7] which is a good pre-
cursor for the synthesis of other new dinuclear molybdenum
complexes, and led to a number of interesting but not al-
ways predictable reactions. More recently, our research has
focused on the reactions of complex 1 with a series of unsat-
urated organic molecules. Reactions of 1 with nitrile mainly
afforded the η2-η2-perpendicularly coordinated nitrile com-
plex, and the resulting nitrile complex underwent CϵN
bond cleavage of acetonitrile to form µ4- and µ5-N MoRu
clusters.[8] The reaction of complex 1 with the allene
H2C=C=CHCO2Me produced two allene-isomerization
products and two allene-coupling products, which is signifi-
cantly different from the reactivity of allene with non-
bridged and singly bridged dinuclear molybdenum carbonyl
complexes.[9] The N–N bond cleavage of diazoalkane
Ar2CN2 following orthometalation of the aryl and dispro-
portionation of CS2 were observed in thermal reactions
with 1.[10] In this contribution, we report the reactions of
complex 1 with a series of phosphanylalkynes PhnP-
(CϵCR)3–n [n = 2, 1, 0; R = Ph, Fc (ferrocenyl, C10H9)],
in which the phosphanylalkynes behaved as disubstituted
Introduction
Phosphanylalkynes are a source of rich chemistry, and
these compounds have been used widely in organometallic
and coordination chemistry. Phosphanylalkynes of the
PPh2CϵCR type are potentially bifunctional ligands, and
they have been shown to react with mononuclear and poly-
nuclear complexes in various ways. Although these ligands
act mostly as P-donor phosphanes and/or the CϵC moiety
towards most transition-metal center(s),[1] there are also
many cases in which they undergo cleavage of the P–C(al-
kyne) bond, which can be induced by thermolysis, photoly-
sis, and chemical activation, to generate separate phosphido
(PPh2) and acetylide (CϵCR) fragments.[2] In some cases,
the subsequent formation of a P–C bond has even been
observed.[3,4] Furthermore, the PPh2CϵCR ligands can in-
sert into reactive M–H and M–C bonds.[2g,5]
Due to the rigidity of the doubly bridged bis(cyclopenta-
dienyl) ligands, the corresponding metal complexes exhibit
[a] State Key Laboratory of Elemento-Organic Chemistry, College
of Chemistry, Nankai University,
Tianjin 300071, People’s Republic of China
Fax: +86-22-23504781
E-mail: bqwang@nankai.edu.cn
[b] State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, People’s Republic of China
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Reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with Phosphanylalkynes
acetylenes, and/or the cleavage of P–C(alkyne) bond and Reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with
rearrangement of phosphanylalkynes into phosphido-sub- Phosphanylalkynes PhnP(CϵCR)3–n (n = 2, 1, 0; R = Ph,
stituted vinylidenyl ligand were observed.
Fc)
When complex 1 reacted with Ph2PCϵCPh in refluxing
toluene, the P–C(alkyne) bond cleavage and phosphanyl-
alkyne rearrangement product (Me2C)(Me2Si)[(η5-C5H3)2-
Mo2(CO)4{µ–η1-η2-C=C(Ph)PPh2}] (3) was obtained in
40% yield, along with two alkyne-bridged complexes
(Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(µ-η2-η2(Ќ)-RCϵCPh)]
[R = Ph2P (2), 10%; Ph2P(O) (4), 5%] (Scheme 2). Al-
though P–C(alkyne) bond cleavage of phosphanylalkynes is
well established,[2] its rearrangement is not.[3] To the best
of our knowledge, the rearrangement of phosphanylalkynes
into phosphido-substituted vinylidenyl ligands by cleavage
of the P–C(alkyne) bond and formation of a P–C(alkene)
bond has not been reported. In the reaction of Ph2PCϵCFc
with complex 1, only the phosphanylalkyne rearrangement
product 5 was isolated in 41% yield.
Results and Discussion
Synthesis and Characterization of Phosphanylalkyne
Ligands PhnP(CϵCR)3–n (R = Ph, Fc; n = 2, 1, 0)
Beletskaya and coworkers demonstrated the synthesis of
phosphanylalkyne ligands by means of cross-coupling reac-
tion of chlorophosphanes PhnPCl3–n with terminal alkynes
catalyzed by cuprous salts.[11] This method also proceeds
smoothly in the synthesis of (ferrocenylethynyl)phosphanes
(Scheme 1). The 1H and 31P NMR spectra of the phosphan-
ylalkyne complexes were in good agreement with the data
previously reported.[11,12] Furthermore, tris(ferrocenylethy-
nyl)phosphane P(CϵCFc)3 was confirmed by X-ray diffrac-
tion analysis (Figure 1).
Both complexes 2 and 4 are deep-brown, air-stable crys-
tals. Complex 2 displays four absorption signals in the IR
spectrum that can be assigned to the terminal carbonyl li-
gands, it also displays three resonances in the 1H NMR
spectrum, which can be assigned to equivalent Cp rings.
1
Complex 4 has IR and H NMR spectra similar to those
of 2, but their 31P{1H} NMR spectra differ greatly. Signals
appear at δ = 19.95 ppm for 2 and δ = 27.71 ppm for 4,
which are both significantly downfield shifted in compari-
son to the signal of Ph2PCϵCPh (δ = –33.50 ppm).[13] It
was reported that phosphanylalkyne itself[14] and phos-
phanylalkyne-bridged metal complexes such as Co2(CO)6-
(µ-Ph2PCϵCt-Bu)[15] and (µ-Ph2PCH2PPh2)Co2(CO)4(µ-
Ph2PCϵCR) (R = Ph, t-Bu, and Ph2P)[16] could be oxidized
to their oxide partly during chromatography. The signal in
the 31P{1H} NMR spectrum of the phosphanylalkyne-
bridged metal complex is also shifted upfield relative to that
of its oxide, for instance, δ = 6.8 ppm for (µ-Ph2PCH2PPh2)-
Co2(CO)4(µ-Ph2PCϵCPh) versus δ = 28.4 ppm for its ox-
ide.[16b] So, complex 4 can be presumed to be the oxide of
2. To confirm this, the reaction of 1 with Ph2P(O)CϵCPh
was examined and complex 4 was obtained as expected. The
P=O bond was reflected by the absorption at 1174 cm–1 in
the IR spectrum.
Scheme 1.
Complex 3 is a deep-orange air-stable crystalline solid.
Four terminal carbonyl absorptions are observed in its IR
1
spectrum. Its H NMR spectrum comprises six resonances
for six Cp protons, revealing that the two Cp ligands are
inequivalent. The 31P{1H} NMR spectrum shows a singlet
at δ = –78.0 ppm, which is significantly upfield shifted from
that found for Ph2PCϵCPh (δ = –33.5 ppm).[13] In ad-
dition, the 13C{1H} NMR spectrum exhibits two signifi-
cantly low-field doublets at δ = 273.1 and 241.4 ppm, which
are even more downfield than the signals for the carbonyl
groups (δ = 238.7–232.9 ppm). All these data suggest that
complex 3 has an unusual structure, which was confirmed
by the single-crystal X-ray diffraction analysis. Complex 5
Figure 1. ORTEP diagram of P(CϵCFc)3. Thermal ellipsoids are
shown at the 30% level. Hydrogen atoms and solvent molecules are
omitted for clarity. Selected bond lengths [Å] and angles [°]: C(31)–
C(32) 1.197(4), C(33)–C(34) 1.206(4), C(35)–C(36) 1.203(4), C(36)–
P(1)–C(34) 99.08(13), C(36)–P(1)–C(32) 99.30(13), C(34)–P(1)–
C(32) 99.80(12).
1
has IR and H and 31P{1H} NMR spectra that are similar
to those of 3, and their structures are very similar as well.
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B. Li, S. Xu, H. Song, B. Wang
FULL PAPER
Scheme 2.
As shown in Scheme 2, the reaction of 1 with bis- by single-crystal X-ray diffraction analysis. The 31P{1H}
(ethynyl)-functionalized phosphanes gave similar products: NMR spectra of the two isomers are greatly different from
alkyne-bridged complex 6 (36%) and phosphanylalkyne re- each other [δ = –41.1 (11a) and –28.3 ppm (11b)]. The
1
arrangement complex 7 (9%) for PhP(CϵCPh)2, alkyne- chemical shifts in the H NMR spectra of the two isomers
bridged complex 8 (8%), alkyne-bridged oxide 10 (16%) are also very distinct: for example, four sets of resonance
and phosphanylalkyne rearrangement complex 9 (17%) for signals of the phenyl protons with a ratio of 1:1:12:1 are
PhP(CϵCFc)2. In the reaction of 1 with tris(ethynyl)-func- shown for 11a, whereas eight sets with a ratio of
tionalized phosphanes, the alkyne-bridged complexes (or 1:3:2:1:3:2:2:1 are shown for 11b (see Experimental Section
and alkyne-bridged oxide) were isolated without the phos- for details). In addition, the signal for the CMe2 equatorial
phanylalkyne rearrangement complex: alkyne-bridged com- methyl protons (δ = 0.72 ppm) of isomer 11b are approxi-
plexes 11a (32%) and 11b (9%) and alkyne-bridged oxide mately 0.7 ppm upfield from the typical one, which might
12 (17%) for P(CϵCPh)3, alkyne-bridged complex 13 be attributable to a pronounced shielding of the equatorial
(23%) for P(CϵCFc)3. All these compounds were charac- methyl group by the nearby conjugated phenyl group. Such
terized by multinuclear NMR spectroscopy, IR spec- a phenomenon was also observed in complexes 2, 4, and 6.
troscopy, and elemental analysis, and the molecular struc- The X-ray structure of 11b, which will be discussed in more
tures of complexes 6, 7, 11a, 11b, and 13 were also deter- detail below (Figure 7b), confirms the close nonbonding in-
mined by single-crystal X-ray diffraction analysis.
teraction between the CMe2 equatorial methyl group and
Except for the four stretching vibrations for the terminal the π system of the phenyl group.
carbonyl ligands, complexes 6–13 exhibit stretching signals
in their IR spectra in the range 2173–2144 cm–1, and this is
in good agreement with the retention of the uncoordinated
ν(CϵC) frequency. In the H NMR spectra, complexes 6–
Molecular Structures
1
9 show six (and five for complex 10) resonances for the Cp
Single-crystal X-ray analysis revealed the final structure
protons, indicating the nonequivalence of the two Cp li- assignment of complex 3. In its unit cell, there are two inde-
gands, whereas complexes 11–13 show three peaks for the pendent molecules that are an enantiomeric pair, and they
equivalent Cp rings as expected for symmetrical structures. differ only slightly in their bond lengths and angles (Fig-
In contrast, the 31P{1H} NMR chemical shifts of these ure 2). The most salient feature is the presence of the
complexes are quite different. The phosphanylalkyne re- C=C(Ph)PPh2 phosphido-substituted vinylidenyl ligand,
arrangement complexes 7 and 9 have 31P{1H} NMR reso- which bridges the Mo–Mo bond through the C(20) atom in
nance signals that are significantly upfield shifted in com- an unsymmetrical fashion [Mo(1)–C(20) 2.325(4) Å,
parison to those of phosphanylalkyne. However, alkyne- Mo(2)–C(20) 1.998(5) Å] and coordinates to Mo(1) through
bridged complexes 6, 8, 11a, 11b, and 13 (including alkyne- the P(1) atom [Mo(1)–P(1) 2.4357(15) Å] as a four-electron
bridged oxides 10 and 12) show 31P{1H} NMR signals that donor. The shorter Mo–Mo distance in 3 [3.1578(6) Å] ver-
are evidently downfield shifted in comparison to those in sus that found in 1 [3.4328(12) Å][7] is probably a conse-
the spectrum of phosphanylalkyne.
quence of the additional bridge. The C(20)–C(21) bond
It is interesting to note that complexes 11a and 11b are length of 1.345(6) Å indicates that it changes from a triple
two isomers of the alkyne [P(CϵCPh)3]-bridged complexes. bond to a double bond, but the torsion angles Mo(2)–
The difference between the isomeric pairs is the location of C(20)–C(21)–P(1) of 173.0° and Mo(2)–C(20)–C(21)–P(1)
the CMe2 and SiMe2 bridging groups, which is confirmed of 167.5° show that the six atoms of the alkene are not
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Reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with Phosphanylalkynes
Figure 2. ORTEP diagram of (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4{µ-η1:η2-C=C(Ph)PPh2}] (3), showing the two crystallographically
independent molecules in the unit cell. Thermal ellipsoids are shown at the 30% level. Hydrogen atoms are omitted for clarity.
well settled in an ideal alkenyl plane. This contributes to
Complexes 5 and 7 have structures similar to that of 3
minimizing the steric interactions between the phenyl group and their molecular structures are depicted in Figures 3 and
and the C(4)–O(4) carbonyl group. Similarly, the phospho- 4, respectively. Selected bond lengths and angles are listed
rus P(1) atom lies 0.4703 Å below the ethenyl plane men- in Table 1. The bond lengths and angles of the Mo2{µ-
tioned above. In the absence of a metal–metal bond, Mo(2) η1:η2-C=CP} core structure in complexes 5 and 7 vary little
formally has 16 valence electrons and Mo(1) has 18 valence compared to those of 3.
electrons. Thus, a dative Mo(1)ǞMo(2) bond achieves the
Single-crystal X-ray analysis of 6 (Figure 5), 11a (Fig-
36-electron bimetallic complex. In addition, one of the four ure 6), 11b (Figure 7), and 13 (Figure 8) confirms that these
carbonyl ligands, C(2)–O(2), adopts a weak semibridging compounds are crosswise-substituted alkyne-bridged com-
coordination to the Mo–Mo bond [ЄMo(1)–C(2)–O(2) plexes. The dimensions of the Mo2C2 core are similar to
167.7(4)°].[17]
those found in the (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(µ-
η2-η2-HCϵCCH2CO2Me)][9] complex and the unbridged
Cp2Mo2(CO)4(µ-RCϵCR) analogue.[18] The alkyne ligands
Figure 4. ORTEP diagram of (Me2C)(Me2Si)[(η5-C5H3)2Mo2-
(CO)4{µ-η1:η2-C=C(Ph)PPh(CϵCPh)}] (7). Thermal ellipsoids are
shown at the 30% level. Hydrogen atoms and solvent molecules are
omitted for clarity.
Figure 3. ORTEP diagram of (Me2C)(Me2Si)[(η5-C5H3)2Mo2-
(CO)4{µ-η1:η2-C=C(Fc)PPh2}] (5). Thermal ellipsoids are shown
at the 30% level. Hydrogen atoms are omitted for clarity.
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B. Li, S. Xu, H. Song, B. Wang
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Table 1. Selected bond lengths [Å] and angles [°] for 3, 5, and 7.
3
5
7
Mo(1)–Mo(2)
Mo(1)–C(20)
Mo(2)–C(20)
C(20)–C(21)
C(21)–P(1)
Mo(1)–P(1)
Mo(2)–C(20)–Mo(1) 93.54(19)
Mo(2)–C(20)–C(21)
Mo(1)–C(20)–C(21)
C(20)–C(21)–P(1)
Mo(1)–P(1)–C(21)
3.1577(7)
2.324(5)
1.999(5)
1.347(7)
1.742(6)
2.4357(15)
3.1785(4)
2.353(2)
2.021(2)
1.352(3)
1.761(2)
2.4477(7)
92.91(9)
155.68(18)
110.68(16)
95.63(16)
93.45(8)
3.1786(7)
2.351(5)
1.989(5)
1.380(7)
1.746(5)
2.4230(14)
93.81(19)
156.8(4)
109.3(3)
93.5(3)
155.4(4)
111.0(4)
94.9(4)
93.28(18)
94.41(16)
in these complexes are all tipped over to the CMe2 bridge
side of the doubly bridged ligand, possibly owing to the
smaller steric effect of the CMe2 bridge than that of the
SiMe2 bridge.
The spectroscopic data of these complexes are consistent
with their structures, except for 11b and 13 (Figures 7 and
8). Both of these compounds show no symmetry in the solid
Figure 5. ORTEP diagram of (Me2C)(Me2Si)[(η5-C5H3)2Mo2-
(CO)4{µ-η2:η2-PhCϵCPPh(CϵCPh)}] (6). Thermal ellipsoids are
shown at the 30% level. Hydrogen atoms and solvent molecules are
omitted for clarity. Selected bond lengths [Å] and angles [°]: Mo(1)–
Mo(2) 2.9293(9), Mo(1)–C(26) 2.211(6), Mo(1)–C(27) 2.162(6),
Mo(2)–C(26) 2.206(6), Mo(2)–C(27) 2.187(5), C(34)–C(35)
1.197(9), Mo(2)–C(26)–Mo(1) 83.09(19), Mo(1)–C(27)–Mo(2)
84.7(2), C(26)–C(27)–C(28) 131.1(5), C(27)–C(26)–P(1) 128.4(4),
C(35)–C(34)–P(1) 174.0(6), C(34)–C(35)–C(36) 176.0(8).
1
state, but in the H NMR spectra, 11b and 13 exhibit three
resonances for the Cp protons, which is suggestive of Cs
symmetry. Therefore, a rotation process about the C(18)–
P(1) bond of complex 11b, which creates a mirror plane that
cuts the whole molecule into two equivalent halves, occurs
in solution. A similar fluxional process is also apparent in
the C(21)–C(22) bond of complex 13 in solution. In com-
plexes 6 and 11b, the phenyl group lies close to the CMe2
bridging group, which accounts for the migration of the
After the structures of all the products were determined
proton peaks of CMe2 to a higher field, as mentioned clearly, we were then interested in the stereochemistry of
above. these complexes. Due to the difference in the CMe2 and
Figure 6. ORTEP diagram of (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4{µ-η2:η2-PhCϵCP(CϵCPh)2}] (11a): (a) viewed perpendicular to the
Mo–Mo bond and (b) viewed down the Mo–Mo axis. Thermal ellipsoids are shown at the 30% level. Hydrogen atoms are omitted for
clarity. Selected bond lengths [Å] and angles [°]: Mo(1)–Mo(1A) 2.9267(7), Mo(1)–C(13) 2.208(4), Mo(1)–C(18) 2.165(4), C(13)–C(18)
1.361(7), C(19)–C(20) 1.194(6), Mo(1)–C(13)–Mo(1A) 83.02(18), Mo(1)–C(18)–Mo(1A) 85.05(19).
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Reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with Phosphanylalkynes
Figure 7. ORTEP diagram of (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4{µ-η2:η2-PhCϵCP(CϵCPh)2}] (11b), showing one of the two crystallo-
graphically independent molecules in the unit cell: (a) viewed perpendicular to the Mo–Mo bond and (b) viewed down the Mo–Mo axis.
Thermal ellipsoids are shown at the 30% level. Hydrogen atoms are omitted for clarity. Selected bond lengths [Å] and angles [°]: Mo(1)–
Mo(2) 2.9403(11), Mo(1)–C(18) 2.220(8), Mo(2)–C(18) 2.201(7), Mo(1)–C(13) 2.197(8), Mo(2)–C(13) 2.181(8), C(13)–C(18) 1.399(14),
C(19)–C(20) 1.189(11), C(29)–C(30) 1.266(14), Mo(2)–C(18)–Mo(1) 83.4(3), Mo(2)–C(13)–Mo(1) 84.4(3), C(18)–C(13)–C(14) 125.8(7),
C(13)–C(18)–P(1) 124.5(6), C(20)–C(19)–P(1) 169.7(8), C(30)–C(29)–P(1) 167.1(8).
SiMe2 bridging groups of precursor 1 and to the fact that
the introduced phosphanylalkyne ligand is inclined to lie to
one side of the doubly bridged ligand, every compound is
chiral. For instance, there are four isomers in theory for
products 2–5 and 11–13 in the reactions of 1 with mono-
or tris(ethynyl)-functionalized phosphanes and even more
isomeric possibilities for products 6–10 of the reactions of
1 with bis(ethynyl)-functionalized phosphanes, as the phos-
phanes in these compounds are also chiral. However, in the
crystal unit cells, an enantiomeric pair was found for 3,
whereas only one isomer was found for 5, 6, 7, and 13. It
is surprising that 11a and 11b are the only isomeric pairs to
be observed. The reason was not very clear, but the steric
distinction between the CMe2 and SiMe2 bridging groups
of precursor 1 is essential for the site of the ligand addition
to the title complex and to the structures of the products.
Conclusions
Figure 8. ORTEP diagram of (Me2C)(Me2Si)[(η5-C5H3)2Mo2-
To conclude, reactions of the doubly bridged bis(cyclo-
(CO)4{µ-η2:η2-FcCϵCP(CϵCFc)2}] (13), showing one of the two
pentadienyl) dinuclear molybdenum complex (Me2C)-
crystallographically independent molecules in the unit cell. Thermal
(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with a series of phosphan-
ellipsoids are shown at the 30% level. Hydrogen atoms are omitted
ylalkynes PhnP(CϵCR)3–n (n = 0, 1, 2; R = Ph, Fc) afforded
not only the normal alkyne-bridged complexes (or and al-
kyne-bridged oxide) but also phosphanylalkyne P–C(al-
kyne) bond cleavage and phosphanylalkyne rearrangement
complexes. It should also be noted that a phosphanylalkyne
rearrangement complex is prominent in the reaction of 1
for clarity. Selected bond lengths [Å] and angles [°]: Mo(1)–Mo(2)
2.956(2), Mo(1)–C(20) 2.216(4), Mo(1)–C(21) 2.219(5), Mo(2)–C(20)
2.205(4), Mo(2)–C(21) 2.291(4), C(20)–C(21) 1.390(6), C(42)–C(43)
1.210(7), C(44)–C(45) 1.206(7), Mo(2)–C(20)–Mo(1) 83.93(16),
Mo(1)–C(21)–Mo(2) 81.90(15), C(20)–C(21)–C(22) 135.7(4), C(21)–
C(20)–P(1) 121.6(3), C(42)–C(43)–P(1) 172.7(4), C(43)–C(42)–C(41)
174.8(5), C(45)–C(44)–P(1) 170.3(5), C(44)–C(45)–C(46) 175.8(5).
Eur. J. Inorg. Chem. 2008, 5494–5504
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5499

B. Li, S. Xu, H. Song, B. Wang
FULL PAPER
5.21 (m, 2 H, Cp-H), 4.87 (t, 2 H, Cp-H), 1.55 (s, 3 H, CMe), 0.63
(s, 3 H, CMe), 0.56 (s, 3 H, SiMe), 0.49 (s, 3 H, SiMe) ppm.
with monoethynyl-functionalized phosphanes, but tris(eth-
ynyl)-functionalized phosphanes behave as disubstituted
acetylenes when treated with complex 1. The mechanism of
the rearrangement of phosphanylalkynes into phosphido-
substituted vinylidenyl ligands is still under study.
31P{1H} NMR (CDCl ): δ = 27.7 (s) ppm. IR: ν = 1994 (s) (νCO),
˜
3
1953 (s) (νCO), 1907 (s) (νCO), 1893 (m) (νCO), 1174 (w) (νP=O) cm–1.
C39H33Mo2O5PSi (835.99): calcd. C 56.26, H 3.99; found C 55.98,
H 4.06.
Reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with Ph2P-
(O)CϵCPh: A solution of 1 (117 mg, 0.20 mmol) and Ph2P(O)-
CϵCPh (90 mg, 0.30 mmol) in toluene (30 mL) was heated at re-
flux for 10 h. During this time the solution turned from deep green
to dark brown. After removal of the solvent, the residue was chro-
matographed on an alumina column. Elution with CH2Cl2/acetone
developed a brown band, which afforded 3 (75 mg, 45% yield) as
brown crystals.
Experimental Section
General Procedures: Schlenk and vacuum-line techniques were em-
ployed for all manipulations. All solvents were distilled from appro-
priate drying agents under an atmosphere of argon prior to use.
Melting points are uncorrected. 1H and 31P{1H} NMR spectra
were recorded with a Bruker AV300 instrument [1H at 300 MHz
and 31P{1H} at 121.5 MHz]. 13C{1H} NMR experiments were car-
ried out with a Varian Mercury VX300 or a Bruker AV400 instru-
ment [13C{1H} at 75.5 or 100 MHz]. All spectra were referenced
to the residual signals of the deuterated solvents. IR spectra were
recorded as KBr disks with a Nicolet 380 FTIR spectrometer. Ele-
mental analyses were performed with a Perkin–Elmer 240C ana-
lyzer. (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1),[7] PhnP(CϵCPh)3–n
(n = 0, 1, 2),[12] Ph2P(O)CϵCPh,[19] and FcCϵCH[20] were prepared
by literature methods.
Reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with
PhP(CϵCPh)2:
A solution of 1 (117 mg, 0.20 mmol) and
PhP(CϵCPh)2 (70 mg, 0.22 mmol) in toluene (30 mL) was heated
at reflux for 6 h. During this time the solution turned from deep
green to dark brown. After removal of the solvent, the residue was
chromatographed on an alumina column by using petroleum ether/
CH2Cl2 as the eluent. The first band (brown) gave 6 (60 mg, 36%
yield) as deep-brown crystals. The second band (purple) gave 7
(15 mg, 9% yield) as brown crystals.
Reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with
1
Complex 6: M.p. 172–3 °C. H NMR (CDCl3): δ = 7.39 (m, 4 H,
Ph2PCϵCPh:
A solution of 1 (117 mg, 0.20 mmol) and
Ph-H), 7.34 (d, J = 1.48 Hz, 1 H, Ph-H), 7.25 (m, 5 H, Ph-H), 7.21
(m, 1 H, Ph-H), 7.18–7.10 (m, 4 H, Ph-H), 5.53 (t, 1 H, Cp-H),
5.40 (t, 1 H, Cp-H), 5.23 (br. s, 1 H, Cp-H), 5.21 (br. s, 1 H, Cp-
H), 4.97 (m, 1 H, Cp-H), 4.93 (m, 1 H, Cp-H), 1.56 (s, 3 H, CMe),
0.69 (s, 3 H, CMe), 0.62 (s, 3 H, SiMe), 0.39 (s, 3 H, SiMe) ppm.
Ph2PCϵCPh (60 mg, 0.21 mmol) in toluene (30 mL) was heated at
reflux for 6 h. During this time the solution turned from deep green
to dark brown. After removal of the solvent, the residue was chro-
matographed on an alumina column. Elution with petroleum ether/
CH2Cl2 gave a brown band and an orange band, which afforded 2
(16 mg, 10% yield) and 3 (65 mg, 40% yield) as brown and deep-
orange crystals, respectively. Elution with CH2Cl2/acetone devel-
oped a brown band, which afforded 4 (8 mg, 5% yield) as brown
crystals.
31P{1H} NMR (CDCl ): δ = –4.3 (s) ppm. IR: ν = 2156 (w) (νCϵC),
˜
3
1989 (s) (νCO), 1949 (s) (νCO), 1920 (s) (νCO), 1893 (m) (νCO) cm–1.
C41H33Mo2O4PSi (844.00): calcd. C 58.58, H 3.96; found C 58.86,
H 3.96.
Complex 7: M.p. 167 °C (decomp.). 1H NMR (CDCl3): δ = 7.59 (t,
1 H, Ph-H), 7.56 (d, J = 1.68 Hz, 2 H, Ph-H), 7.43 (m, 2 H, Ph-
H), 7.40 (br. s, 2 H, Ph-H), 7.39–7.33 (m, 5 H, Ph-H), 7.27 (m, 2
H, Ph-H), 7.08 (t, 1 H, Ph-H), 5.95 (m, 1 H, Cp-H), 5.76 (t, 1 H,
Cp-H), 5.47 (t, 1 H, Cp-H), 5.30 (br. s, 1 H, Cp-H), 5.15 (m, 1 H,
Cp-H), 5.11 (t, 1 H, Cp-H), 1.50 (s, 3 H, CMe), 1.38 (s, 3 H, CMe),
0.70 (s, 3 H, SiMe), 0.63 (s, 3 H, SiMe) ppm. 13C{1H} NMR
(75.5 MHz, CDCl3): δ = 273.7 [d, J = 33.2 Hz, Ph(CϵCPh)P(Ph)-
C=CMo2], 239.6 [d, JC,P = 36.4 Hz, Ph(CϵCPh)P(Ph)C=CMo2],
238.0, 235.7, 232.7, 232.6 (CO), 148.5 (d, JC,P = 52.1 Hz, Ph),
145.3, 136.2 (Cp), 132.6, 131.8, 131.4, 130.7, 130.6, 130.5, 130.4,
129.2, 129.0, 128.9, 128.4, 125.7, 123.6, 123.4, 121.3 (Ph), 106.3 (d,
J = 6.3 Hz), 105.9 (d, J = 4.7 Hz), 100.4 (Cp), 100.1 (d, J = 10.4 Hz,
PCϵCPh), 92.8, 89.0, 86.8 (d, J = 13.6 Hz), 85.9 (d, J = 13.6 Hz),
85.0 (d, J = 5.9 Hz, Cp), 81.9 (d, JC,P = 50.9 Hz, PCϵCPh), 38.3
(d, J = 7.1 Hz, CMe2), 36.3 (CMe2), 24.2 (d, J = 6.6 Hz, CMe2),
4.4, 0.6 (SiMe2) ppm. 31P{1H} NMR (CDCl3): δ = –102.9 (s) ppm.
Complex 2: M.p. 166 °C (decomp.). 1H NMR (CDCl3): δ = 7.58 (t,
5 H, Ph-H), 7.37–7.20 (m, 10 H, Ph-H), 5.46 (br. s, 2 H, Cp-H),
5.28 (br. s, 2 H, Cp-H), 4.98 (br. s, 2 H, Cp-H), 1.57 (s, 3 H, CMe),
0.65 (s, 3 H, CMe), 0.64 (s, 3 H, SiMe), 0.42 (s, 3 H, SiMe) ppm.
31P{1H} NMR (CDCl ): δ = 19.9 (s) ppm. IR: ν = 1985 (s) (νCO),
˜
3
1946 (s) (νCO), 1914 (s) (νCO), 1893 (s) (νCO
)
cm–1.
C39H33Mo2O4PSi (820.00): calcd. C 57.36, H 4.07; found C 57.57,
H 4.35.
1
Complex: 3: M.p. 178–9 °C. H NMR (CDCl3): δ = 7.67 (m, 2 H,
Ph-H), 7.50 (m, 3 H, Ph-H), 7.31–7.14 (m, 9 H, Ph-H), 7.05 (t, 1
H, Ph-H), 5.93 (m, 1 H, Cp-H), 5.75 (t, 1 H, Cp-H), 5.12 (t, 1 H,
Cp-H), 5.09 (m, 1 H, Cp-H), 4.94 (t, 1 H, Cp-H), 3.85 (m, 1 H,
Cp-H), 1.38 (s, 3 H, CMe), 1.28 (s, 3 H, CMe), 0.73 (s, 3 H, SiMe),
0.58 (s, 3 H, SiMe) ppm. 13C{1H} NMR (75.5 MHz, CDCl3): δ =
273.1 [d, J = 31.3 Hz, Ph2P(Ph)C=CMo2], 241.4 [d, JC,P = 35.7 Hz,
Ph2P(Ph)C=CMo2], 238.7, 235.6, 233.0, 232.9 (CO), 147.2 (d, JC,P
= 46.6 Hz, Ph), 144.7, 137.2 (Cp), 134.8 (d, J = 30.8 Hz), 132.9 (d,
JC,P = 45.1 Hz), 131.7, 131.6, 131.2, 131.1, 130.4, 130.0, 129.0,
128.9, 128.8, 128.6, 128.1, 125.4, 123.6, 123.5 (Ph), 105.5 (d, J =
5.2 Hz), 99.2, 98.9 (d, JC,P = 4.2 Hz), 92.1, 89.1, 86.3 (d, J =
15.1 Hz), 85.7 (d, J = 13.7 Hz), 85.0 (d, J = 16.0 Hz, Cp), 37.7 (d,
J = 7.8 Hz, CMe2), 35.8 (CMe2), 23.8 (d, J = 7.3 Hz, CMe2), 4.1,
0.2 (SiMe2) ppm. 31P{1H} NMR (CDCl3): δ = –78.0 (s) ppm. IR:
IR: ν = 2159 (m) (νCϵC), 1958 (s) (νCO), 1925 (s) (νCO), 1981 (s)
˜
(νCO), 1848 (m) (νCO) cm–1. C41H33Mo2O4PSi (844.00): calcd. C
58.58, H 3.96; found C 58.53, H 3.87.
Reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with P(Cϵ
CPh)3: A solution of 1 (117 mg, 0.20 mmol) and P(CϵCPh)3
(103 mg, 0.31 mmol) in toluene (30 mL) was heated at reflux for
5 h. During this time the solution turned from deep green to dark
brown. After removal of the solvent, the residue was chromato-
graphed on an alumina column by using petroleum ether/CH2Cl2
as the eluent. The first band (brown) gave 11a (56 mg, 32% yield)
as deep-brown crystals. The second band (brown) gave 11b (16 mg,
9% yield) as brown crystals. Elution with CH2Cl2/acetone devel-
ν = 1955 (s) (νCO), 1921 (s) (νCO), 1871 (s) (νCO), 1843 (m) (νCO
)
˜
cm–1. C39H33Mo2O4PSi (820.00): calcd. C 57.36, H 4.07; found C
57.22, H 4.18.
Complex 4: M.p. 214 °C (decomp.). 1H NMR (CDCl3): δ = 7.62
(m, 5 H, Ph-H), 7.34–7.18 (m, 10 H, Ph-H), 5.33 (t, 2 H, Cp-H),
5500
www.eurjic.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 5494–5504

Reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with Phosphanylalkynes
oped a brown band, which afforded 12 (30 mg, 17% yield) as green
perature for 15 h. Then, the resulting ammonium salt was removed
crystals.
by filtration, and the solvent was evaporated under reduced pres-
sure. The crude product was then chromatographed on an alumina
column by using petroleum ether/CH2Cl2 as the eluent. The first
band (yellow) afforded unreacted FcCϵCH (0.12 g). The second
band (orange) gave P(CϵCFc)3 (0.61 g, 66% yield with respect to
consuming FcCϵCH) as orange crystals. Data for P(CϵCFc)3:[11]
1
Complex 11a: M.p. 195 °C (decomp.). H NMR (CDCl3): δ = 7.93
(m, 1 H, Ph-H), 7.90 (m, 1 H, Ph-H), 7.36–7.24 (m, 12 H, Ph-H),
7.14 (t, 1 H, Ph-H), 5.45 (t, 2 H, Cp-H), 5.41 (m, 2 H, Cp-H), 5.28
(m, 2 H, Cp-H), 1.69 (s, 3 H, CMe), 1.62 (s, 3 H, CMe), 0.66 (s, 3
H, SiMe), 0.47 (s, 3 H, SiMe) ppm. 31P{1H} NMR (CDCl3): δ =
1
M.p. 205 °C (decomp.). H NMR (CDCl3): δ = 4.55 (m, 6H, Cp-
–41.1 (s) ppm. IR: ν = 2154 (w) (νCϵC), 1993 (s) (νCO), 1944 (s)
˜
H), 4.26 (m, 21H, Cp-H) ppm. 31P{1H} NMR (CDCl3): δ = –87.8
(νCO), 1921 (s) (νCO), 1893 (s) (νCO) cm–1. C43H33Mo2O4PSi
(s) ppm.
(868.00): calcd. C 59.73, H 3.85; found C 59.51, H 4.05.
Reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with
Ph2P(CϵCFc) (Fc = ferrocenyl, C10H9Fe): A solution of 1 (117 mg,
0.20 mmol) and Ph2PCϵCFc (87 mg, 0.22 mmol) in toluene
(30 mL) was heated at reflux for 6 h. During this time the solution
turned from deep green to dark brown. After removal of the sol-
vent, the residue was chromatographed on an alumina column.
Elution with petroleum ether/CH2Cl2 gave an orange band, which
afforded 5 (75 mg, 41% yield) as brown crystals.
1
Complex 11b: M.p. 218 °C (decomp.). H NMR (CDCl3): δ = 7.37
(m, 1 H, Ph-H), 7.34 (m, 3 H, Ph-H), 7.33 (t, 2 H, Ph-H), 7.32 (s,
1 H, Ph-H), 7.25 (m, 3 H, Ph-H), 7.23 (m, 2 H, Ph-H), 7.08 (t, 2
H, Ph-H), 6.98 (t, 1 H, Ph-H), 5.56 (t, 2 H, Cp-H), 5.27 (m, 2 H,
Cp-H), 5.03 (m, 2 H, Cp-H), 1.59 (s, 3 H, CMe), 0.72 (s, 3 H,
CMe), 0.64 (s, 3 H, SiMe), 0.44 (s, 3 H, SiMe) ppm. 31P{1H} NMR
(CDCl ): δ = –28.3 (s) ppm. IR: ν = 2158 (w) (νCϵC), 1994 (s)
˜
3
(νCO), 1959 (s) (νCO), 1925 (s) (νCO), 1897 (s) (νCO) cm–1.
C43H33Mo2O4PSi (868.00): calcd. C 59.73, H 3.85; found C 59.41,
H 4.07.
Complex 5: M.p. 226 °C (decomp.). 1H NMR (CDCl3): δ = 7.75
(m, 2 H, Ph-H), 7.50 (br. s, 3 H, Ph-H), 7.39 (br. s, 3 H, Ph-H),
7.29 (m, 2 H, Ph-H), 5.82 (m, 1 H, Cp-H), 5.58 (br. s, 1 H, Cp-H),
5.07 (t, 1 H, Cp-H), 5.02 (br. s, 1 H, Cp-H), 4.82 (t, 1 H, Cp-H),
4.71 (s, 1 H, Fc-H), 4.24 (s, 1 H, Fc-H), 4.08 (s, 1 H, Fc-H), 3.91
(s, 1 H, Fc-H),3.73 (br. s, 1 H, Cp-H), 3.53 (s, 5 H, Fc-H), 1.31 (s,
3 H, CMe), 1.18 (s, 3 H, CMe), 0.73 (s, 3 H, SiMe), 0.55 (s, 3 H,
SiMe) ppm. 13C{1H} NMR (75.5 MHz, CDCl3): δ = 270.5 [br. s,
Ph2P(Fc)C=CMo2], 242.5 [d, JC,P = 34.9 Hz, Ph2P(Fc)C=CMo2],
239.3, 238.2, 233.9, 233.8 (CO), 143.1 (Cp), 136.8, 136.4, 133.7,
132.9, 132.8, 131.6, 131.4, 131.3, 130.5, 130.2, 128.8, 128.7, 128.6
(Ph), 104.9.1, 100.2 (d, J = 8.0 Hz), 97.1, 91.9, 88.0, 86.2 (d, J =
15.8 Hz), 86.0 (d, J = 17.1 Hz), 85.2 (d, J = 17.1 Hz, Cp), 69.7,
69.6, 68.0, 66.7, 65.0, 64.1 (br. s, Fc), 38.64 (d, J = 7.4 Hz, CMe2),
35.7 (CMe2), 24.1 (d, J = 6.4 Hz, CMe2), 4.2, 0.4 (SiMe2) ppm.
1
Complex 12: M.p. 248 °C (decomp.). H NMR (CDCl3): δ = 7.75
(s, 1 H, Ph-H), 7.72 (s, 1 H, Ph-H), 7.36–7.20 (m, 15 H, Ph-H),
7.06 (t, 1 H, Ph-H), 5.70 (br. s, 2 H, Cp-H), 5.55 (t, 2 H, Cp-H),
5.28 (m, 2 H, Cp-H), 1.67 (s, 3 H, CMe), 1.65 (s, 3 H, CMe), 0.69
(s, 3 H, SiMe), 0.49 (s, 3 H, SiMe) ppm. 31P{1H} NMR (CDCl3):
δ = –1.3 (s) ppm. IR: ν = 2173 (m) (νCϵC), 1998 (s) (νCO), 1952
˜
(s) (νCO), 1924 (s) (νCO), 1897 (m) (νCO), 1199 (m) (νP=O) cm–1.
C43H33Mo2O5PSi (883.99): calcd. C 58.65, H 3.78; found C 58.50,
H 3.82.
Preparation of the Ph2–nP(CϵCFc)n (Fc = ferrocenyl, n = 0, 1, 2)
Ligand: Ligands Ph2–nP(CϵCFc)n (n = 0, 1, 2) were synthesized by
using the method for the preparation of Ph2–nP(CϵCPh)n (n = 0,
1, 2).[12] A solution of Ph2PCl (1.10 g, 5.00 mmol), Et3N (3.10 g,
15 mmol), FcCϵCH (1.05 g, 5.00 mmol), and CuI (10 mg,
0.05 mmol) in toluene (30 mL) was mixed in a Schlenk flask and
stirred at room temperature overnight. Then, the resulting ammo-
nium salt was removed by filtration, and the solvent was evapo-
rated under reduced pressure. The crude product was then chro-
matographed on an alumina column by using petroleum ether/
CH2Cl2 as the eluent. The resulting orange band gave Ph2PCϵCFc
(1.15 g, 60% yield) as orange solids. Data for Ph2PCϵCFc:[11] M.p.
31P{1H} NMR (CDCl ): δ = –77.2 (s) ppm. IR: ν = 1948 (s) (νCO),
˜
3
1909 (s) (νCO), 1869 (s) (νCO), 18430 (s) (νCO
)
cm–1.
C43H37FeMo2O4PSi (927.97): calcd. C 55.61, H 4.02; found C
55.52, H 4.29.
Reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with
PhP(CϵCFc)2 (Fc = ferrocenyl, C10H9Fe): A solution of 1 (117 mg,
0.20 mmol) and PhP(CϵCFc)2 (130 mg, 0.25 mmol) in toluene
(30 mL) was heated at reflux for 6 h. During this time the solution
turned from deep green to dark brown. After removal of the sol-
vent, the residue was chromatographed on an alumina column.
Elution with petroleum ether/CH2Cl2 gave a brown band and an
orange band, which afforded 8 (18 mg, 8% yield) and 9 (38 mg,
17% yield) as brown crystals, respectively. Elution with CH2Cl2/
acetone developed a brown band, which afforded 10 (35 mg, 16%
yield) as brown crystals.
Complex 8: M.p. 182 °C (decomp.). 1H NMR (CDCl3): δ = 7.90 (t,
2 H, Ph-H), 7.38 (m, 3 H, Ph-H), 5.53 (br. s, 1 H, Cp-H), 5.46 (t,
1 H, Cp-H), 5.26 (t, 1 H, Cp-H), 5.22 (m, 1 H, Cp-H), 5.08 (m, 1
H, Cp-H), 4.69 (m, 1 H, Cp-H), 4.55 (m, 3 H, Fc-H), 4.33 (m, 6
H, Fc-H), 4.29 (m, 9 H, Fc-H), 1.46 (s, 3 H, CMe), 0.97 (s, 3 H,
CMe), 0.55 (s, 3 H, SiMe), 0.37 (s, 3 H, SiMe) ppm. 31P{1H} NMR
1
96–7 °C. H NMR (CDCl3): δ = 7.66 (m, 4H, Ph-H), 7.35 (m, 6H,
Ph-H), 4.54 (t, 2H, Cp-H), 4.25 (t, 2H, Cp-H), 4.23 (m, 2H, Cp-
H) ppm. 31P{1H} NMR (CDCl3): δ = –32.8 (s) ppm.
A solution of PhPCl2 (0.45 g, 2.50 mmol), Et3N (3.10 g, 15 mmol),
FcCϵCH (1.05 g, 5.00 mmol), and CuI (10 mg, 0.05 mmol) in tolu-
ene (30 mL) was mixed in a Schlenk flask and stirred at room tem-
perature for 16 h. Then, the resulting ammonium salt was removed
by filtration, and the solvent was evaporated under reduced pres-
sure. The crude product was then chromatographed on an alumina
column by using petroleum ether/CH2Cl2 as the eluent. The first
band (yellow) afforded unreacted FcCϵCH (0.20 g). The second
band (orange) gave PhP(CϵCFc)2 (0.78 g, 72% yield with respect
to consuming FcCϵCH) as orange crystals. Data for PhP(Cϵ
(CDCl ): δ = –11.2 (s) ppm. IR: ν = 2154 (m) (νCϵC), 1976 (s)
˜
3
(νCO), 1892 (s) (νCO), 1831 (m) (νCO) cm–1. C49H41Fe2Mo2O4PSi
CFc)2:[11] M.p. 142–3 °C. H NMR (CDCl3): δ = 7.84 (m, 2H, Ph-
1
(1059.93): calcd. C 55.71, H 3.91; found C 55.80, H 4.39.
Complex 9: M.p. 193–194 °C. 1H NMR (CDCl3): δ = 7.51 (m, 2 H,
H), 7.44 (m, 3H, Ph-H), 4.53 (br. s, 4H, Cp-H), 4.24 (br. s, 14H,
Cp-H) ppm. 31P{1H} NMR (CDCl3): δ = –59.4 (s) ppm.
Ph-H), 7.40 (m, 3 H, Ph-H), 5.91 (m, 1 H, Cp-H), 5.63 (br. s, 1 H,
A solution of PCl3 (0.22 g, 1.60 mmol), Et3N (3.00 g, 14.4 mmol), Cp-H), 5.44 (t, 1 H, Cp-H), 5.30 (br. s, 1 H, Cp-H), 5.13 (m, 1 H,
FcCϵCH (1.01 g, 4.81 mmol), and CuI (10 mg, 0.05 mmol) in tolu-
ene (30 mL) was mixed in a Schlenk flask and stirred at room tem-
Cp-H), 5.00 (t, 1 H, Cp-H), 4.67 (m, 2 H, Fc-H), 4.46 (s, 1 H, Fc-
H), 4.38 (br. s, 2 H, Fc-H), 4.31 (s, 4 H, Fc-H), 4.27 (s, 1 H, Fc-
Eur. J. Inorg. Chem. 2008, 5494–5504
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5501

B. Li, S. Xu, H. Song, B. Wang
FULL PAPER
H), 4.14 (s, 1 H, Fc-H), 4.10 (s, 1 H, Fc-H), 4.07 (br. s, 1 H, Fc-
H), 3.92 (s, 5 H, Fc-H), 1.51 (s, 3 H, CMe), 1.48 (s, 3 H, CMe), 0.70
(s, 3 H, SiMe), 0.62 (s, 3 H, SiMe) ppm. 13C{1H} NMR (100 MHz,
(Cp),78.5 (d, JC,P = 52.0 Hz, FcCϵCP), 72.4, 70.3, 70.0, 69.2, 69.1,
67.6 (d, J = 8.5 Hz), 66.9 (d, J = 9.0 Hz), 64.9 (br. s), 63.9 (br., s),
62.2, 62.1 (Fc), 38.3 (d, J = 4.9 Hz, CMe2), 35.9 (CMe2), 24.3 (d,
J = 4.8 Hz, CMe2), 4.2, 0.4 (SiMe2) ppm. 31P{1H} NMR (CDCl3):
CDCl3): δ = 270.0 [br. s, PhP(FcCϵC)C=CMo2], 240.1 [d, JC,P
=
36.5 Hz, Ph2P(FcCϵC)C=CMo2], 239.4, 236.8, 233.6, 233.5 (CO), δ = –101.6 (s) ppm. IR: ν = 2146 (m) (νCϵC), 1957 (s) (νCO), 1924
˜
144.7 (Cp), 130.9, 130.4, 128.8, 128.6 (Ph), 107.7 (d, J = 7.1 Hz, (s) (νCO), 1878 (s) (νCO), 1844 (m) (νCO) cm–1. C49H41Fe2Mo2O4PSi
FcCϵCP), 107.6, 105.5, 100.7, 99.4, 92.7, 88.1, 86.6, 85.3, 84.8 (1059.93): calcd. C 55.71, H 3.91; found C 55.07, H 4.25.
Table 2. Crystal data and summary of X-ray data collection for 3, 5, 6, and 7.
3
5
6·CH2Cl2
7·0.5CH2Cl2
Empirical formula
Fw
T [K]
C39H33Mo2O4PSi
816.59
294(2)
C43H37FeMo2O4PSi
924.52
294(2)
C42H35Cl2Mo2O4PSi
925.54
294(2)
C41.50H34ClMo2O4PSi
883.08
294(2)
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
triclinic
P1
monoclinic
P2(1)/c
12.2776(15)
16.5610(19)
19.052(2)
90
98.600(2)
90
3830.2(8)
4
triclinic
P1
monoclinic
P2(1)/n
11.3110(12)
21.936(3)
16.8453(18)
90
103.255(2)
90
4068.3(8)
4
¯
¯
13.542(2)
14.150(2)
19.359(4)
102.949(8)
98.072(7)
90.435(7)
3576.4(11)
4
12.251(3)
12.690(3)
14.223(3)
111.546(3)
96.514(4)
103.295(4)
1953.1(7)
2
γ [°]
V [Å3]
Z
Dcalcd. [gcm–3]
1.517
0.819
1.603
1.134
1.574
0.892
1.442
0.789
µ [mm–1]
F(000)
1648
0.26ϫ0.20ϫ0.12
52.36
19701
13878/0.0329
855
0.853
0.0424, 0.0982
0.0857, 0.1239
1864
0.22ϫ0.16ϫ0.12
52.78
21856
7830/0.0218
469
1.064
0.0254, 0.0582
0.0365, 0.0649
932
1780
0.22ϫ0.20ϫ0.16
52.88
22869
8338/0.0385
497
1.074
0.0445, 0.1321
0.0792, 0.1524
Crystal size [mm]
Max. 2θ [°]
Reflections collected
Independent reflns/Rint
No. of parameters
GOF on F2
R1, wR2 [IϾ2σ(I)]
R1, wR2 (all data)
Largest peak in final
diff. map [e Å–3]
0.26ϫ0.20ϫ0.18
52.80
11005
7854/0.0334
483
1.033
0.0539, 0.1322
0.1013, 0.1623
0.621
0.811
1.597
1.014
Table 3. Crystal data and summary of X-ray data collection for 11a, 11b, 13, and P(CϵCFc)3.
11a
11b
13·0.5CH2Cl2
P(CϵCFc)3
Empirical formula
Fw
T [K]
C43H33Mo2O4PSi
864.63
294(2)
C43H33Mo2O4PSi
864.63
113(2)
C55.50H46ClFe3Mo2O4PSi C36H27Fe3P
1230.86
294(2)
658.10
113(2)
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
orthorhombic
Pnma
12.6571(15)
16.744(2)
18.014(2)
90
90
90
3817.8(8)
4
1.504
monoclinic
P2(1)/c
19.278(3)
25.060(6)
15.893(4)
90
90.341(9)
90
7678(3)
8
triclinic
P1
monoclinic
P2(1)/a
13.2787(7)
11.0982(5)
19.1156(11)
90
92.081(3)
90
2815.2(3)
4
¯
10.428(7)
15.217(10)
18.545(12)
102.600(10)
103.423(10)
107.828(10)
2589(3)
γ [°]
V [Å3]
Z
2
Dcalcd. [gcm–3]
1.496
0.767
1.579
1.442
1.553
1.607
µ [mm–1]
0.772
F(000)
1744
0.24ϫ0.22ϫ0.16
52.76
20809
4042/0.0408
251
1.008
0.0314, 0.0699
0.0666, 0.0877
3488
0.24ϫ0.20ϫ0.18
55.70
43835
16295/0.0854
930
1.091
0.0717, 0.1794
0.0868, 0.2096
1238
0.22ϫ0.20ϫ0.14
50.04
12927
8938/0.0227
622
1.064
0.0375, 0.1059
0.0557, 0.1205
1344
0.14ϫ0.12ϫ0.12
55.76
25862
6710/0.0525
362
1.105
0.0461, 0.0957
0.0561, 0.1028
Crystal size [mm]
Max. 2θ [°]
Reflections collected
Independent reflns/Rint
No. of parameters
GOF on F2
R1, wR2 [IϾ2σ(I)]
R1, wR2 (all data)
Largest peak in final
diff. map [e Å–3]
0.647
1.807
1.083
0.464
5502
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 5494–5504

Reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with Phosphanylalkynes
1
inde, M. T. Moreno, Inorg. Chem. 2004, 43, 8185–8198; g) E.
Stulz, S. M. Scott, A. D. Bond, S. Otto, J. K. M. Sanders, Inorg.
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226–233; i) T. Baumgartner, K. Huynh, S. Schleidt, A. J.
Lough, I. Manners, Chem. Eur. J. 2002, 8, 4622–4632; j) E.
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5268; k) J. H. Berenguer, M. Bernechea, J. Fornies, J. Gómez,
E. Lalinde, Organometallics 2002, 21, 2314–2324; l) J. Forniés,
A. García, J. Gómez, E. Lalinde, M. T. Moreno, Organometal-
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Fujiwara, M. D. Vargas, D. Braga, F. Grepioni, Organometal-
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506, 121–127; t) I. Moldes, J. Ros, Inorg. Chim. Acta 1995, 232,
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Fornies, E. Lalinde, A. Martín, M. T. Morenob, A. J. Welch, J.
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Weinmann, M. Winter, M. Leise, W. Imhof, J. Organomet.
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465–481 and references cited therein.
Complex 10: M.p. 179–180 °C. H NMR (CDCl3): δ = 7.59 (m, 2
H, Ph-H), 7.34 (t, 1 H, Ph-H), 7.26 (m, 2 H, Ph-H), 5.60 (t, 1 H,
Cp-H), 5.54 (br. s, 1 H, Cp-H), 5.50 (br. s, 1 H, Cp-H), 5.49 (br. s,
1 H, Cp-H), 5.30 (s, 1 H, Cp-H), 5.25 (t, 1 H, Cp-H), 4.47 (br. s,
2 H, Fc-H), 4.26 (m, 2 H, Fc-H), 4.24 (s, 1 H, Fc-H), 4.19 (s, 5 H,
Fc-H), 4.17 (s, 5 H, Fc-H), 3.97 (br. s, 1 H, Fc-H), 3.84 (br. s, 2 H,
Fc-H), 1.64 (s, 3 H, CMe), 1.51 (s, 3 H, CMe), 0.67 (s, 3 H, SiMe),
0.50 (s, 3 H, SiMe) ppm. 31P{1H} NMR (CDCl3): δ = 24.4 (s) ppm.
IR: ν = 2160 (m) (νCϵC), 2000 (m) (νCO), 1949 (s) (νCO), 1920 (s)
˜
(νCO), 1888 (m) (νCO), 1191 (w) (νP=O) cm–1. C49H41Fe2Mo2O5PSi
(1075.93): calcd. C 54.65, H 3.84; found C 54.86, H 3.92.
Reaction of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with
P(CϵCFc)3 (Fc = ferrocenyl, C10H9Fe): A solution of 1 (117 mg,
0.20 mmol) and P(CϵCFc)3 (145 mg, 0.22 mmol) in toluene
(30 mL) was heated at reflux for 6 h. During this time the solution
turned from deep green to dark brown. After removal of the sol-
vent, the residue was chromatographed on an alumina column.
Elution with petroleum ether/CH2Cl2 gave a brown band, which
afforded 13 (55 mg, 23% yield) as brown crystals.
1
Complex 13: M.p. 205 °C (decomp.). H NMR (CDCl3): δ = 5.64
(br. s, 2 H, Cp-H), 5.48 (t, 2 H, Cp-H), 5.23 (br. s, 2 H, Cp-H),
4.52 (br. s, 6 H, Fc-H), 4.32 (s, 4 H, Fc-H), 4.28 (br. s, 17 H, Fc-
H), 1.66 (s, 6 H, CMe), 0.62 (s, 3 H, SiMe), 0.37 (s, 3 H, SiMe)
ppm. 31P{1H} NMR (CDCl ): δ = –37.4 (s) ppm. IR: ν = 2144
˜
3
(m) (νCϵC), 1976 (s) (νCO), 1946 (s) (νCO), 1909 (s) (νCO) cm–1.
C55H45Fe3Mo2O4PSi (1191.90): calcd. C 55.37, H 3.81; found C
55.19, H 4.01.
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Crystallographic Studies: Single crystals of all complexes suitable
for X-ray diffraction were obtained from hexane/CH2Cl2. Data col-
lection of complexes 3, 5, 6, 7, 11a, and 13 were performed with a
Bruker SMART 1000 at 294(2) K, whereas those of 11b and
P(CϵCFc)3 were performed with a Rigaku Saturn 70 equipped
with a rotating anode system at 113(2) K by using graphite-mono-
chromated Mo-Kα radiation (ω-2θ scans, λ = 0.71073 Å). Semiem-
pirical absorption corrections were applied for all complexes. The
structures were solved by direct methods and refined by full-matrix
least-squares. All calculations were performed with the SHELXL-
97 program system. The molecular structures of 6, 7, and 13 con-
tained CH2Cl2 molecules of solvation. The crystal data and sum-
mary of X-ray data collection are presented in Tables 2 and 3.
CCDC-636554 (for 3), -689564 (for 5), -689565 (for 6), -689566 (for
7), -689567 (for 11a), -689568 (for 11b), -689831 (for 13), and
-689569 [for P(CϵCFc)3] contain the supplementary crystallo-
graphic data. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
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Acknowledgments
This work was financially supported by the National Natural Sci-
ence Foundation of China (Grants 20574036, 20702026, 20721062)
and the Specialized Research Fund for the Doctoral Program of
Higher Education (Grant 20050055008).
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Published Online: November 5, 2008
5504
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Eur. J. Inorg. Chem. 2008, 5494–5504