Osmium-mediated hexamerization of phenylacetylene

Article abstract of DOI:10.1002/anie.200601542

(Chemical Equation Presented) A larger oligomer: Although transition-metal-mediated reactions of alkynes to give dimers, trimers, tetramers, and polymers are well-known, reactions of alkynes to give well-defined oligomers of medium molecular weight (e.g. pentamers, hexamers) are very scarce. The selective hexamerization of HC≡CPh in the reaction with [OsCl(PCP)(PPh₃)] (PCP = 2,6-(Ph₂PCH₂) ₂C₆H₃; see scheme) is a rare example thereof.

Full text of DOI:10.1002/anie.200601542

Communications
ne,[9a–c] vinylvinylidene,[9d–e] benzene,[10] fulvene,[11–13] hexadie-
nyne,[14] and unusual ligands derived from the tetramerization
of alkynes.[15] In contrast, reactions of alkynes to give
selectively well-defined oligomers of medium molecular
weight (for example, pentamers, hexamers) of alkynes,
either stoichiometric or catalytic in nature, are very
scarce.[16] Herein we report a rare example of selective
ꢀ
hexamerization of HC CPh to give bimetallic osmium
complexes with bridging m-1,2-bis(h5-cyclopentadienyl)-1,2-
diphenyl-ethane ligands from the reaction of [OsCl(PCP)-
ꢀ
(PPh3)] (PCP = 2,6-(Ph2PCH2)2C6H3) with HC CPh.
ꢀ
Treatment of [OsCl(PCP)(PPh3)] (1) with excess HC
CPh in benzene rapidly produced a brownish solution of the
vinylidene complex [OsCl( C CHPh)(PCP)(PPh3)] (2).
[17]
= =
When the solution was left standing, complex 2 was consumed
gradually. After four days, the reaction produced an orange-
red precipitate and a dark brown solution. The orange-red
precipitate was identified to be the racemic mixture of the
(R,R) and (S,S) isomers of the dicationic bimetallic complex 4
(Scheme 1). From the filtrate, the neutral bimetallic complex
5 and a small amount of the cationic monomeric complex 3
could be isolated (Scheme 1). The reaction of isolated
ꢀ
vinylidene complex 2 with excess HC CPh gave the same
result.
Complex 3 has been characterized by elemental analysis,
FAB-MS, and multinuclear NMR spectroscopy. The structure
has also been confirmed by an X-ray diffraction study.[18] The
molecular structure of the complex cation of 3, shown in
Figure 1, clearly reveals that the complex is a four-legged
piano stool cyclopentadienyl osmium(IV) complex with a
facially bound PCP ligand and a chloride ligand. The solution
NMR spectroscopic data are consistent with the solid-state
structure. The facial arrangement of the PCP ligand in 3 is
worth noting. Numerous complexes with PCP and related
ligands have been reported in recent years.[19] In most of these
reported complexes, the PCP and related ligands usually
adopt a meridional geometry. Complex 3 represents a rare
example of a PCP complex with a facially arranged PCP li-
gand.[20]
Alkyne Oligomerization
DOI: 10.1002/anie.200601542
Osmium-Mediated Hexamerization of
Phenylacetylene**
Ting Bin Wen, Zhong Yuan Zhou, and Guochen Jia*
Transition-metal-mediated oligomerization and polymeri-
zation reactions of alkynes are attractive atom-economical
À
C C bond-formation reactions for organic and organometal-
lic synthesis. Previous studies have led to the discovery of
catalysts that can mediate selective dimerization,[1] trimeriza-
tion,[2–4] tetramerization,[5,6] and polymerization[7] of alkynes.
Parallel to this development, a number of organometallic
complexes derived from dimerization, trimerization, and
tetramerization of alkynes have been isolated, including
interesting metallacycles,[8] complexes with cyclobutadie-
The most interesting result from the reaction of 1 with
ꢀ
HC CPh is the formation of the bimetallic complexes 4 and 5,
which contain a m-1,2-bis(h5-cyclopentadienyl)-1,2-diphenyl-
ethane bridging ligand (Scheme 1). The bridging ligand is
ꢀ
formally derived from selective hexamerization of HC CPh.
As a result of the different configurations (R or S) of the
CHPh carbon atoms, both the neutral and dicationic com-
plexes are expected to have (R,R), (S,S), and meso stereoiso-
mers. Experimentally, all three isomers of the neutral com-
plex 5 have been isolated and identified: the meso isomer 5c
was obtained as a yellow solid, and the (R,R) isomer 5a and
(S,S) isomer 5b were obtained in the form of a racemic
mixture. For the cationic complex, we have isolated the (R,R)
and (S,S) isomers (4a and 4b) as a racemic mixture.
[*] Dr. T. B. Wen, Prof. Dr. G. Jia
Department of Chemistry
The Hong Kong University of Science and Technology
Clear Water Bay
Kowloon, Hong Kong (P.R. China)
Fax: (+852)2358-7361
E-mail: chjiag@ust.hk
The structures of all these bimetallic complexes have been
determined by X-ray diffraction. As an illustration, the
molecular structures of cationic complex 4a ((R,R) isomer),
neutral complexes 5a ((R,R) isomer), and 5c (meso isomer)
are shown in Figures 2, 3, and 4, respectively. Complex 4a has
crystallographic C2 symmetry with the twofold axis passing
Prof. Z. Y. Zhou
Department of Applied Biology and Chemical Technology
Hong Kong Polytechnic University
Hung Hum, Hong Kong (P.R. China)
[**] This work was supported by the Hong Kong Research Grant Council
(HKUST6090/02P).
5842
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angewandte
Chemie
As indicated by the plausible mechanism shown
in Scheme 2, complexes 3, 4, and 5 could all be
formed through the fulvene intermediate
derived from a formal [2+2+1] cyclotrimerization
D
ꢀ
ꢀ
of HC CPh. Thus, reaction of 1 with HC CPh
= =
produces the vinylidene complex [OsCl( C
CHPh)(PPh3)(PCP)] (2), which has been con-
firmed experimentally. Complex 2 could dissociate
the PPh3 ligand in solution to give the unsaturated
vinylidene A. Complex A undergoes a cycloaddi-
ꢀ
tion reaction with HC CPh to give first the metal-
lacyclobutene complex B and then the metallacy-
clohexadiene complex C, which could undergo a
reductive elimination to give the h4-fulvene com-
plex D. Protonation of D at the exocyclic CHPh
carbon atom would give 3. Couplings of vinylidenes
[21]
=
at M C bonds with alkynes are known reactions.
Although relatively rare, formation of fulvene
metal complexes from formal [2+2+1] cyclotrime-
rizations of terminal alkynes has been reported in
the stoichiometric reactions of rhodium,[11] iri-
dium,[12] and palladium[13] complexes with alkynes.
ꢀ
It is interesting to note that HC CR is dimerized
on related metal fragments such as {Cp*Ru} (or
{CpRu}; Cp* = C5Me5, Cp = C5H5) and {TpRu}
(Tp = hydrotris(pyrazolyl)borate) to give metalla-
cyclopentadienes by oxidative coupling,[8b,c] or
=
vinylvinylidenes by coupling of vinylidenes at C
C bonds with alkynes.[9d,e]
The fulvene intermediate D could undergo an
intramolecular electron transfer (or “electron tau-
tomerism”) to generate the transient cyclopenta-
dienyl osmium complex E, featuring an OsIII center
Scheme 1. Synthesis of complexes 3–5.
Figure 1. Molecular structure for the cation of 3. The PPh2 phenyl rings
of the PCP ligands are omitted for clarity.
Figure 2. Molecular structure for the cation of 4a ((R,R) isomer). The
PPh2 phenyl rings of the PCP ligands are omitted for clarity.
through the midpoint of C06 and C06A. The meso complex 5c
has idealized Ci symmetry with the crystallographic inversion
center at the midpoint of C06 and C06A. All the complexes
contain a facially bound PCP ligand. The solid-state struc-
tures are supported by their solution NMR spectroscopic
data.
and a carbon-centered radical, which then undergoes inter-
molecular radical coupling to produce the paramagnetic
OsIII complex F. The 19-electron OsIII species F may undergo
Angew. Chem. Int. Ed. 2006, 45, 5842 –5846
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5843

Communications
generated by deprotonation of 3 with NEt3. Following the
proposed mechanism, one would expect that the reaction of 1
ꢀ
with PhC CH would lead to the formation of a mixture of
(R,R), (S,S), and meso stereoisomers for both neutral and
cationic complexes. Experimentally, we have isolated and
identified all three isomers of the neutral complex 5, though
meso isomer 5c was obtained in a relatively low yield. For the
cationic complexes, we have been able to isolate and
characterize the (R,R) and (S,S) isomers 4a and 4b. In line
with the low yield of 5c, isolation of the dicationic meso
isomer 4c was not successful. It is noted that only racemic
isomers of bis(ferroceniumyl)ethane were obtained in the
dimerization reaction of [Cp*Fe(C5H4CHPh)]+.[23b]
In summary, reaction of [OsCl(PPh3)(PCP)] with excess
ꢀ
HC CPh led to the unprecedented formation of bimetallic
osmium complexes containing
a
m-1,2-bis(h5-cyclopenta-
Figure 3. Molecular structure for 5a ((R,R) isomer). The PPh2 phenyl
dienyl)-1,2-diphenyl-ethane bridging ligand, which are pre-
sumably formed through a fulvene intermediate which is
rings of the PCP ligands are omitted for clarity.
ꢀ
generated from a formal [2+2+1] cylotrimerization of HC
CPh.
Experimental Section
A mixture of [OsCl(PPh3)(PCP)] (0.80 g, 0.83 mmol) and phenyl-
acetylene (1.40 mL, 12.7 mmol) in benzene (12 mL) was stirred at
room temperature for 4 days to give an orange-red precipitate and a
dark brown solution. The orange-red solid was collected by filtration,
washed with benzene (2mL) and diethyl ether (2” 5 mL), dried in a
vacuum overnight, and was identified to be a racemic mixture of 4a
and 4b. Yield: 221 mg, 26%. The benzene washings and the mother
liquid were collected and combined. The solution was concentrated to
about 1 mL to give 3 as an orange-yellow crystalline solid, which was
collected by filtration, washed with benzene (1 mL) and diethyl ether
(2” 2mL), and dried in a vacuum overnight. Yield: 95 mg, 11%. The
filtrate and the benzene washings were again combined and reduced
to about 0.5 mL. Addition of diethyl ether (20 mL) to the residue
provided a brownish-yellow solid, which was isolated by filtration and
dried in a vacuum. The solid was then recrystallized from a small
amount of benzene to give a racemic mixture of 5a and 5b as a yellow
microcrystalline solid. Yield: 88 mg, 11%. The solvent of the final
filtrate obtained above was removed in a vacuum. The residue was
washed with hexane (2” 20 mL) to give a brown solid, which was
dried under vacuum and recrystallized from a small amount of
benzene to give 5c as a yellow microcrystalline solid. Yield: 29 mg,
3.5%.
Figure 4. Molecular structure for 5c (meso isomer). The PPh2 phenyl
rings of the PCP ligands are omitted for clarity.
disproportionation to give the neutral OsII complex 5 and the
dicationic OsIV complex 4 with ClÀ as the counteranion.
Radical dimerization involving coordinated fulvene has been
proposed previously, for example, in the reaction of [CpCo-
(C2H4)2] with 6,6-dimethylpentafulvene to give paramagnetic
(1,1,2,2-tetramethyl-1,2-ethanediyl)biscobaltocene,[22] and in
the dimerization of ferrocenylmethyl carbocations to give the
paramagetic iron(III) 1,2-bis(ferroceniumyl)ethane com-
plexes.[23]
Consistent with this proposition, treatment of vinylidene
3: 31P{1H} NMR (121.5 MHz, CD2Cl2): d = 7.6 ppm (s); 1H NMR
(300.13 MHz, CD2Cl2): d = 2.71 (s, 2H, CH2Ph), 4.42(dd, J(PH) =
14.2Hz, J(HH) = 16.2Hz, 2H, PCP-C H2), 4.57 (d, J(HH) = 16.2Hz,
2H, PCP-CH2), 6.66 (s, 2H, Cp-CH), 6.78–7.84 ppm (m, 38H, PPh2,
C6H3, C6H5); 13C{1H} NMR (100.4 MHz, CD2Cl2): d = 147.9 (t,
J(PC) = 6.6 Hz, Os-C(aryl)), 137.5–124.5 (m, other aromatic carbon
atoms), 114.1 (s, Cp-CCH2Ph), 108.4 (s, 2Cp-CPh), 90.6 (s, 2Cp- CH),
43.9 (dd, J(PC) = 23.1, 19.8 Hz, PCP-CH2), 32.8 ppm (s, CH2Ph);
FAB-MS (m-nitrobenzyl alcohol (NBA)): m/z: 1007.8 ([MÀCl]+,
calcd 1007.2). Elemental analysis (%) calcd for
ꢀ
complex 2 with HC CPh in benzene in the presence of added
HEt3NCl produced 3 as the major product [Eq. (1)]. Isolated
3 readily undergoes H/D exchange with D2O to give CD2Ph-
deuterated [D2]-3, thus suggesting that the transient inter-
mediate D can be generated by deprotonation of 3. Treatment
of 3 with NEt3 can also produce the bimetallic complexes 4
and 5, presumably via the fulvene intermediate D that is
C56H46Cl2P2Os: C 64.55, H 4.45; found: C 64.29,
H 4.67.
Racemic isomers 4a and 4b: 31P{1H} NMR
(121.5 MHz, CD2Cl2): d = 9.1 (d), 5.2(d),
J(PP) = 18.4 Hz;
1H NMR
(300.13 MHz,
CD2Cl2): d = 2.97 (dd, J(HH) = 15.3 Hz,
J(PH) = 3.1 Hz, 1H, PCP-CH2), 3.63 (t,
J(PH) = 15.3 Hz, J(HH) = 15.3 Hz, 1H, PCP-
CH2), 3.79 (s, 1H, CHPh), 4.45 (t, J(PH) =
5844
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ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 5842 –5846

Angewandte
Chemie
5c: 31P{1H} NMR (121.5 MHz, CD2Cl2,
298 K): d = 29.2 (br), 22.9 ppm (d (unresolved),
J(PP) = 13.2Hz); (300.13 MHz,
1H NMR
CD2Cl2, 298 K): d = 3.29 (brs, 1H, CHPh),
3.41–3.55 (m, 3H, PCP-CH2), 3.94 (br s, 1H,
Cp-CH), 4.19 (t, J(HH) = 14.4 Hz, J(PH) =
13.4 Hz, 1H, PCP-CH2), 4.32(br s, 1H, Cp-
CH), 5.81–7.37 ppm (m, 38H, PPh2, C6H3,
C6H5); 13C{1H} NMR (100.4 MHz, CD2Cl2):
d = 165.7 (br, Os-C(aryl)), 147.6–120.0 (m,
other aromatic carbon atoms), 96.7 (brs, Cp),
95.0 (s, Cp), 85.5 (s, Cp-CH), 80.5 (brs, Cp-CH),
79.0 (brs, Cp), 51.2(d, J(PC) = 48.5 Hz, PCP-
CH2), 51.0 (s, CHPh), 48.4 ppm (d, J(PC) =
42.3 Hz, PCP-CH2); FAB-MS (NBA): m/z:
1941.0 (M+, calcd 1942.5). Elemental analysis
(%) calcd for C112H90P4Os2: C 69.33, H 4.68;
found: C 69.27, H 5.15.
Received: April 19, 2006
Published online: July 31, 2006
Keywords: alkynes · fulvene ·
.
oligomerization · osmium ·
vinylidene ligands
[1] See, for example: a) W. Weng, C. Guo, R.
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L. A. Oro, Organometallics 2005, 24,
2722; c) J. Le Paih, S. Derien, B. Demerse-
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15.8 Hz, J(HH) = 15.8 Hz, 1H, PCP-CH2), 5.54 (s, 1H, Cp-CH), 6.08–
7.88 (m, 39H, PPh2, C6H3, C6H5, 1H of PCP-CH2 at ca. 7.1 ppm
1
(obscured by aromatic proton resonances, assigned by H,1H COSY
and 1H,13C COSY NMR experiments)), 8.98 (s, 1H, Cp-CH);
13C{1H} NMR (100.4 MHz, CD2Cl2): d = 149.0 (dd, J(PC) = 35.7,
10.4 Hz, Os-C(aryl)), 134.0–122.9 (m, other aromatic carbon atoms),
116.3 (s, Cp), 110.9 (d, J(PC) = 5.9 Hz, Cp), 107.1 (d, J(PC) = 7.4 Hz,
Cp), 89.9 (d, J(PC) = 4.5 Hz, Cp-CH), 87.2(d, J(PC) = 5.9 Hz, Cp-
CH), 54.3 (s, CHPh, hidden under CD2Cl2 resonance, confirmed by
DEPT-135, 1H,13C COSY experiments), 45.9 (d, J(PC) = 41.6 Hz,
PCP-CH2), 45.0 ppm (d, J(PC) = 41.7 Hz, PCP-CH2); FAB-MS
24, 4330; e) H. Katayama, H. Yari, M. Tanaka, F. Ozawa, Chem.
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b) U. Radhakrishnan, V. Gevorgyan, Y. Yamamoto, Tetrahedron
Lett. 2000, 41, 1971.
[4] Formation of linear trimers: a) H. F. Klein, M. Mager, S.
Isringhausen-Bley, U. Florker, H. J. Haupt, Organometallics
1992, 11, 3174; b) A. Haskel, J. Q. Wang, T. Straub, T. G.
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M. S. Eisen, Chem. Eur. J. 2002, 8, 5384.
(NBA): m/z: 2012.0 ([MÀ2Cl]+, calcd 2012.5), 1006.3 ([MÀ2Cl]2+
,
calcd 1006.2). Elemental analysis (%) calcd for C112H90Cl4P4Os2:
C 64.61, H 4.36; found: C 64.76, H 4.50.
Racemic isomers 5a and 5b: 31P{1H} NMR (121.5 MHz, CD2Cl2):
d = 30.7 (d), 15.8 ppm (d), J(PP) = 13.9 Hz; 1H NMR (300.13 MHz,
CD2Cl2): d = 3.04 (s, 1H, CHPh), 3.07 (dd, J(HH) = 14.6 Hz, J(PH) =
5.8 Hz, 1H, PCP-CH2), 3.48 (dd, J(HH) = 13.8 Hz, J(PH) = 5.6 Hz,
1H, PCP-CH2), 3.78 (t, J(HH) = 13.8 Hz, J(PH) = 13.3 Hz, 1H, PCP-
CH2), 4.01 (dd, J(HH) = 14.6, J(PH) = 12.8 Hz, 1H, PCP-CH2), 4.32
(brs, 1H, Cp-CH), 4.59 (brs, 1H, Cp-CH), 5.62–7.47 ppm (m, 38H,
PPh2, C6H3, C6H5); 13C {1H} NMR (100.4 MHz, CD2Cl2): d = 167.0 (t,
J(PC) = 6.6 Hz, Os-C(aryl)), 147.1–119.7 (m, other aromatic carbon
atoms), 96.4 (s, Cp), 91.2(d, J(PC) = 6.5 Hz, Cp), 88.1 (s, Cp-CH),
85.4 (d, J(PC) = 8.2Hz, Cp- CH), 78.9 (d, J(PC) = 13.2Hz, Cp), 50.1
(d, J(PC) = 44.5 Hz, PCP-CH2), 49.0 (s, CHPh), 48.4 ppm (d, J(PC) =
42.9 Hz, PCP-CH2); FAB-MS (NBA, m/z): 1942.3 (M+, calcd 1942.5).
Elemental analysis (%) calcd for C112H90P4Os2: C 69.33, H 4.68;
found: C 69.50, H 4.69.
[5] Cyclotetramerization: B. E. Straub, C. Gollub, Chem. Eur. J.
2004, 10, 3081, and reference therein.
[6] Catalytic linear tetramerization: a) A. D. Burrows, M. Green,
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3104.
[7] J. P. Claverie, R. Soula, Prog. Polym. Sci. 2003, 28, 619, and
references therein.
Angew. Chem. Int. Ed. 2006, 45, 5842 –5846
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5845

Communications
[8] Metallacyclopentadienes: a) E. A. Ison, K. A. Abboud, J. M.
21.203(3) Š, a = 113.654(3), b = 91.597(3), g = 95.632(3)8, V=
4517.1(9) Š3, Z = 2, 1calcd = 1.489 gcmÀ3, m(MoKa) = 2.991 mmÀ1
F(000) = 2032, qmax = 25.008, 20231 reflections, 14998 independ-
ent (Rint = 0.0847), R1 = 0.0416, wR2 = 0.0615 for 1090 parame-
ters and 7745 reflections with I > 2s(I). Crystal data for 5c:
Boncella, Organometallics 2006, 25, 1557; b) Y. Yamamoto, T.
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Alvarez, M. Gomez, M. Paneque, C. M. Posadas, M. L. Poveda,
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Angew. Chem. Int. Ed. 2001, 40, 1951; .
,
C
112H90Os2P4·C6H6 (from saturated benzene solution), Mr =
¯
2018.23, triclinic, space group P1, a = 11.290(5), b = 12.564(6),
c = 19.052(9) Š,
a = 92.669(12),
b = 96.504(11),
g =
114.198(10)8, V= 2436(2) Š3, Z = 1, 1calcd = 1.376 gcmÀ3
,
m-
(MoKa) = 2.720 mmÀ1, F(000) = 1016, qmax = 27.728, 16710 reflec-
tions, 11080 independent (Rint = 0.0713), R1 = 0.0587, wR2 =
0.1266 for 556 parameters and 6682 reflections with I > 2s(I).
Single-crystal X-ray diffraction data were collected on a Bruker
SMART CCD area detector with graphite-monochromated
MoKa radiation at 293 K. All of the data sets were corrected
for absorption with the SADABS program (G. M. Sheldrick,
SADABS). All structures were solved by direct methods,
expanded by difference Fourier syntheses, and refined by full-
matrix least squares on F2 using the Bruker SHELXTL
(Version 5.10) program package. Non-H atoms were refined
anisotropically, except for the disordered CH2Cl2 solvent mol-
[9] See, for example: a) R. Gleiter, D. B. Weiz, Organometallics
2005, 24, 4316; b) C. Schaefer, D. B. Werz, T. H. Staeb, R.
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Valerga, Organometallics 2000, 19, 1333.
[10] See, for example: a) Y. Yamamoto, T. Arakawa, R. Ogawa, K.
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Caulton, C. Chardon, M. L. Doublet, O. Eisenstein, S. A.
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contain the supplementary crystallographic data for this paper.
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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[18] Crystal data for 3: C56H46ClOsP2·0.5CH2Cl2 (from CH2Cl2/
hexane), Mr = 1084.43, monoclinic, space group P21/n, a =
15.626(2), b = 38.941(5), c = 15.771(2) Š, b = 104.365(4)8, V=
9296(2) Š3, Z = 8, 1calcd = 1.550 gcmÀ3, m(MoKa) = 3.023 mmÀ1
F(000) = 4344, qmax = 26.008, 55082reflections, 18265 independ-
ent (Rint = 0.1267), R1 = 0.0520, wR2 = 0.0742for 1119 parame-
,
ters and 6519 reflections with I > 2s(I). Crystal data for 4a:
112H90Cl4Os2P4·1.5CH2Cl2 (from CH2Cl2/hexane), Mr =
C
2209.30, monoclinic, space group C2/c, a = 30.714(4), b =
22.381(3), c = 14.4277(18) Š, b = 92.770(3)8, V= 9906(2) Š3,
Z = 4, 1calcd = 1.481 gcmÀ3
, , F(000) =
m(MoKa) = 2.865 mmÀ1
4420, qmax = 27.578, 33649 reflections, 11418 independent
(Rint = 0.1004), R1 = 0.0617, wR2 = 0.1560 for 573 parameters
and 4689 reflections with I > 2s(I). Crystal data for 5a:
C
112H90Os2P4·CH2Cl2 (from CH2Cl2/hexane), Mr = 2025.05, tri-
¯
clinic, space group P1, a = 13.1359(16), b = 17.841(2), c =
5846 www.angewandte.org
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Angew. Chem. Int. Ed. 2006, 45, 5842 –5846