Photolytic ring-opening polymerization of phosphorus-bridged [1]ferrocenophane coordinating to an organometallic fragment

Article abstract of DOI:10.1021/om000453c

Manganese and tungsten complexes bearing a strained phosphorus-bridged [1]ferrocenophane were prepared by reaction of their appropriate THF complexes with (1,1′-ferrocenediyl)phenylphosphine (1). The monomer complexes [Mn(η⁵-C₅H₄R)(CO)₂(1)] (R = Me, H) and [W(CO)₅(1)] thus obtained were found to undergo a ring-opening polymerization (ROP) upon irradiation with UV-vis light for 10 min in THF or acetonitrile. Because they polymerize in the same manner as the free ligand 1, with the metallic fragment intact, the photopolymerization reaction is considered applicable to a variety of organometallic fragments bearing 1 as a ligand.

Full text of DOI:10.1021/om000453c

Organometallics 2000, 19, 5005-5009
5005
P h otolytic Rin g-Op en in g P olym er iza tion of
P h osp h or u s-Br id ged [1]F er r ocen op h a n e Coor d in a tin g to
a n Or ga n om eta llic F r a gm en t
Tsutomu Mizuta, Makoto Onishi, and Katsuhiko Miyoshi*
Department of Chemistry, Graduate School of Science, Hiroshima University,
1-3 Kagamiyama, Higashi-Hiroshima 739-8526, J apan
Received May 30, 2000
Manganese and tungsten complexes bearing a strained phosphorus-bridged [1]ferro-
cenophane were prepared by reaction of their appropriate THF complexes with (1,1′-
ferrocenediyl)phenylphosphine (1). The monomer complexes [Mn(η5-C5H4R)(CO)2(1)] (R )
Me, H) and [W(CO)5(1)] thus obtained were found to undergo a ring-opening polymerization
(ROP) upon irradiation with UV-vis light for 10 min in THF or acetonitrile. Because they
polymerize in the same manner as the free ligand 1, with the metallic fragment intact, the
photopolymerization reaction is considered applicable to a variety of organometallic fragments
bearing 1 as a ligand.
Sch em e 1
The field of organometallic polymers has attracted
considerable interest because of their potential in
catalysis and synthesis, and as advanced materials.1
One important subclass of this field is related to
pendant-type polymers, in which organometallic frag-
ments are attached to a polymer backbone.2 Phosphine
polymers have often been used as such a backbone,
owing to their versatile ability to bind a variety of metal
fragments.3
Generally, such a pendant-type organometallic poly-
mer is synthesized through the reaction of a metal
fragment with a phosphine polymer prepared in ad-
vance (route a in Scheme 1). An alternative route is the
polymerization of a monomeric complex having a phos-
phine ligand which possesses a functional group for
polymerization (route b). The latter method has the
advantage of giving a well-defined organometallic poly-
mer, since the primary structure of the polymer can be
controlled by designing the monomeric species. In
contrast, the phosphine polymer used in route a may
offer not only monodentate phosphine sites to a metal
fragment but also bi-, tri-, and multidentate sites, to
give an organometallic polymer with low regularity.
One of the potential methods for the polymerization
of a phosphine ligand is the ring-opening reaction of a
strained cyclic substructure. For example, phenylphos-
phirane and phenylphosphetane (PhP(CH2)nCH2; n )
1, 2) have strained three- and four-membered rings,
respectively, which thermally polymerize to give phos-
phine polymers.4 Recently, Manners et al. reported that
phosphorus-bridged [1]ferrocenophane 1 polymerizes
upon heating above 120 °C or upon addition of RLi as
the initiator for living anionic polymerization (eq 1).5,6
(1) (a) Pittman, C. U., J r.; Carraher, C. E., J r.; Reynolds, J . R. In
Organometallic Polymers, Encyclopedia of Polymer Science and Engi-
neering; 2nd ed.; Wiley: New York, 1987; Vol. 10, p 541. (b) Inorganic
and Organometallic Polymers: Macromolecule, Containing Silicon,
Phosphorus, and other Inorganic Elements; Zeldin, M., Wynne, K. J ,
Allcock, H. R., Eds.; ACS Symposium Series 360; American Chemical
Society: Washington, DC, 1988. (c) Nguyen, P.; Gomez-Elipe, P.;
Manners, I. Chem. Rev. 1999, 99, 1515.
(2) (a) Wright, M. E. Macromolecules 1989, 22, 3256. (b) Wright,
M. E.; Cochran, B. B. Organometallics 1993, 12, 3873. (c) Albagli, D.;
Bazan, G.; Wrighton, M. S. Schrock, R. R. J . Am. Chem. Soc. 1992,
114, 4150. (d) Albagli, D.; Bazan, G.; Schrock, R. R. Wrighton, M. S.
Mol. Cryst. Liq. Cryst. 1992, 216, 123. (e) Abd-El-Aziz, A. S.; Denus,
C. R. J . Chem. Soc., Chem. Commun. 1994, 663.
Although the organometallic complexes having these
(4) (a) Cremer, S. E.; Chorvat, R. J . J . Org. Chem. 1967, 32, 4066.
(b) Cremer, S. E.; Cowles, J . M.; Farr, F. R.; Hwang, H.; Kremer, P.
W.; Peterson, A. C.; Gray, G. A. J . Org. Chem. 1992, 57, 511. (c)
Mathey, F. Chem. Rev. 1990, 90, 997. (d) Mathey, F.; Charrier, C.;
Maigrot, N.; Marietti, A.; Ricard, L.; Huy, N. H. T. Comments Inorg.
Chem. 1992, 13, 61. (e) Tumas, W.; Huang, J . C.; Fanwick, P. E.;
Kubiak, C. P. Organometallics 1992, 11, 2944.
(3) For example, (a) Abdulla, K. A.; Allen, N. P.; Badran, A. H.;
Burns, R. P.; Dwyer, J .; McAuliffe, C. A.; Toma, N. D. A. Chem. Ind.
(London) 1976, 273. (b) Grubbs, R. H. CHEMTECH 1977, 512. (c)
Clark, H. C.; Davies, J . A.; Fyfe, C. A.; Hayes, P. J .; Wasylishen, R. E.
Organometallics 1983, 2, 177. (d) Clark, H. C.; Fyfe, C. A.; Hayes, P.
J .; McMahon, I.; Davies, J . A.; Wasylishen, R. E. J . Organomet. Chem.
1987, 322, 393. (e) Siu, A. F. H.; Kane-Maguire, L. A. P.; Pyne, S. G.;
Lambrecht, R. H. J . Chem. Soc., Dalton Trans. 1996, 3747 and
references therein.
(5) (a) Honeyman, C. H.; Foucher, D. A.; Dahmen, F. Y.; Rulkens,
R.; Lough, A. J .; Manners, I. Organometallics 1995, 14, 5503. (b)
Honeyman, C. H.; Peckham, T. J .; Massey, J . A.; Manners, I. J . Chem.
Soc., Chem. Commun. 1996, 2589. (c) Peckham, T. J .; Massey, J . A.;
Honeyman, C. H.; Manners, I. Macromolecules 1999, 32, 2830. (d)
Peckham, T. J .; Lough, A. J .; Manners, I. Organometallics 1999, 18,
1030.
(6) Withers, H. P., J r.; Seyferth, D.; Fellmann, J . D.; Garrou, P. E.;
Martin, S. Organometallics 1982, 1, 1283.
10.1021/om000453c CCC: $19.00 © 2000 American Chemical Society
Publication on Web 10/25/2000

5006 Organometallics, Vol. 19, No. 24, 2000
Mizuta et al.
strained phosphine ligands are known,7 none of them
successfully polymerizes under the above reaction con-
ditions, probably because severe reaction conditions or
reactive species present in the polymerization destroy
the monomeric or oligomeric organometallic fragments.5d
During the course of our study on the reactivity of
phosphorus-bridged [1]ferrocenophane metal complexes,8
we found that the ring-opening reaction took place upon
UV irradiation to give polymers of these complexes. The
successful results obtained under mild reaction condi-
tions prompted us to search for a versatile method for
the polymerization of the organometallic complexes
bearing the strained phosphorus-bridged [1]ferro-
cenophane.
F igu r e 1. Molecular structure of 4. Selected bond lengths
(Å) and angles (deg): W-P ) 2.492(1), W-C17 ) 2.027-
(6), W-C18 ) 2.040(4), W-C19 ) 2.038(4), W-C20 )
2.040(4), W-C21 ) 2.050(3), P-C1 ) 1.843(3), P-C6 )
1.832(4), P-C11 ) 1.814(3); P-W-C17 ) 177.0(2), P-W-
C18 ) 89.5(1), P-W-C19 ) 87.1(2), P-W-C20 ) 94.1(1),
P-W-C21 ) 86.1(1), W-P-C1 ) 118.0(1), W-P-C6 )
119.6(1), W-P-C11 ) 113.9(1), C1-P-C6 ) 94.0(2), C1-
P-C11 ) 103.5(2), C1-P-C6 ) 105.0(2).
Resu lts a n d Discu ssion
The monomer complexes [Mn(η5-C5H4R)(CO)2(1)] (3a ,
R ) Me; 3b, R ) H) and [W(CO)5(1)] (4) were prepared
by the reaction of 1 with [Mn(η5-C5H4R)(CO)2(THF)] and
[W(CO)5(THF)],7a,9 respectively. The 1H, 13C, and 31P
NMR and IR spectra of 3a and 3b were consistent with
the structures expected, and those of 4 were identical
with those reported previously by Seyferth and Withers.7a
In the 13C{1H} NMR spectra of these three complexes,
a doublet assignable to the ipso carbons of the ferrocene
moiety was observed at considerably high field, i.e., 28.5
ppm (J CP ) 15 Hz) (3a ), 28.3 ppm (J CP ) 16 Hz) (3b),
or 21.1 ppm (J CP ) 15 Hz) (4), and these doublets are
characteristic of the strained [1]ferrocenophane struc-
ture.10
F igu r e 2. Definition of structural parameters for [1]-
ferrocenophanes.
The molecular structure of 4 was also confirmed by
X-ray analysis, as shown in Figure 1, where five CO
ligands and 1 form an octahedral geometry around a
tungsten center. The W-CO bond trans to the W-P
bond is slightly shorter than the other four W-CO
bonds, because the former CO ligand receives more
effective back-donation than others from the organo-
metallic fragment.11 The deformation angles R, â, and
θ for the strained [1]ferrocenophane unit are defined
in Figure 2. The tilt angle R is 25.6°, and the two â
angles are 33.6 and 35.5°. Since these deformation
parameters are comparable to R ) 26.9° and â ) 32.3°
for the free 1,12 it is confirmed that the strain in the
[1]ferrocenophane unit is almost intact upon coordina-
tion to the metal fragment.
5 is irradiated with UV light in the presence of an F-
source such as PF6-, the new complex 6 is formed,
though in a limited yield, as a ring-opening product of
the phosphorus-bridged [1]ferrocenophane (eq 2). Since
the fluorinated phosphine ligand in 6 is formed due to
the F- anion present, the products of a similar reaction
in the absence of the F- source are of interest. Thus,
the photolysis was carried out with neutral isostructural
complexes, [Mn(η5-C5H4R)(CO)2(1)] (3a , R ) Me; 3b, R
) H).
A THF solution of 3a was irradiated for 10 min with
UV light through a Pyrex filter. The 31P{1H} NMR
spectrum of the THF solution showed that the resonance
at 111.1 ppm of the starting 3a disappeared completely
and that a relatively sharp new signal appeared at 74.0
ppm. A similar reaction in acetonitrile gave similar
results, whereas those in CH2Cl2, 1,2-dichloroethane,
benzene, and THF containing CCl4 as an additive gave
rise to complicated 31P{1H} NMR spectra.
We previously reported the photoreaction of the cat-
ionic iron complex [FeCp(CO)2(1)]+ (5) in CH2Cl2.8 When
(7) (a) Seyferth, D.; Withers, H. P., J r. Organometallics 1982, 1,
1275. (b) Butler, I. R.; Cullen, W. R.; Rettig, S. J . Organometallics 1987,
6, 872. (c) Mercier, F.; Deschamps, B.; Mathey, F. J . Am. Chem. Soc.
1989, 111, 9098. (d) Bader, A.; Pathak, D. D.; Wild, S. B.; Willis, A. C.
J . Chem. Soc., Dalton Trans. 1992, 1751. (e) Hung, J .-T.; Yang, S.-W.;
Gray, G. M.; Lammertsma, K. J . Org. Chem. 1993, 58, 6786. (f) Kang,
Y. B.; Pabel, M.; Willis, A. C.; Wild, S. B. J . Chem. Soc., Chem.
Commun. 1994, 475. (g) Hung, J .-T.; Yang, S.-W.; Chand, P.; Gray, G.
M.; Lammertsma, K. J . Am. Chem. Soc. 1994, 116, 10966. (h) Bader,
A.; Kang, Y. B.; Pabel, M.; Pathak, D. D.; Willis, A. C.; Wild, S. B.
Organometallics 1995, 14, 1434. (i) Lammertsma, K.; Wang, B.; Hung,
J .-T.; Ehlers, A. W.; Gray, G. M. J . Am. Chem. Soc. 1999, 121, 11650.
(8) Mizuta, T.; Yamasaki, T.; Nakazawa, H.; Miyoshi, K. Organo-
metallics 1996, 15, 1093.
(9) (a) Herrmann, W. A.; Kneuper, H.-J .; Herdtweck, E. Chem. Ber.
1989, 122, 433. (b) Herrmann, W. A.; Kneuper, H.-J .; Herdtweck, E.
Chem. Ber. 1989, 122, 445.
(10) Manners, I. Adv. Organomet. Chem. 1995, 37, 131.
(11) Aroney, M. J .; Buys, I. E.; Davies, M. S.; Hambley, T. W. J .
Chem. Soc., Dalton Trans. 1994, 2827.
The product isolated from the THF solution was
1
formulated as 7a and was characterized by IR and H,
13C, and 31P NMR spectra as well as by an elemental

Polymerization of p-Bridged [1]Ferroceneophane
Organometallics, Vol. 19, No. 24, 2000 5007
analysis. In the ν(CO) infrared region, two strong peaks
sulfur, the products having a major singlet at 38.2 ppm
in 31P{1H} NMR were separated with a preparative-
scale GPC column and then examined using an analyti-
cal GPC column. The estimated molecular weights were
as follows: Mw ) 1.1 × 104 and Mn ) 1.9 × 103. Other
sulfurized products having minor signals were sepa-
rated further by the preparative GPC column using a
recycling mode. Finally, a dimer (9) and a trimer (10)
of 1 were separately isolated as crystalline materials.
X-ray structural analyses indicated that they have cyclic
structures.13
were observed at 1926 and 1862 cm-1. These were
almost comparable to the peaks at 1930 and 1864 cm-1
of the starting 3a , indicating not only that neither of
the two carbonyl groups left the manganese moiety but
also that the electronic environments of the two carbonyl
groups were similar in 3a and 7a . The 1H NMR
spectrum showed considerably broad resonances, but
their integrated intensities agreed with those expected
for the Ph, Me, and three C5H4 groups. In the 31P{1H}
NMR spectrum, the resonance shifted from 111.1 ppm
for the starting 3a to 74.0 ppm. This upfield shift is
characteristic of the polymerization of the phosphorus-
bridged [1]ferrocenophane. For example, the resonance
of 1 shifts from 13.3 ppm to -31.7 ppm in the thermal
and living anionic ring-opening polymerization (eq 1),5a,6
and for the cationic phosphenium-bridged [1]ferro-
cenophane, the resonance shifts from 37.5 to 23.8 ppm.5d
Elemental analysis of 7a supported a formula identical
with that of the starting 3a . GPC indicated that the
product possessed an approximate weight-average mo-
lecular weight (Mw) of 3700 and a number-average mole-
cular weight (Mn) of 2000. The molecular weight distri-
bution was wide, from 450 to 2.0 × 104, with a polydis-
persity of 1.9. The results for 3b were essentially the
same as those for 3a , though the product 7b had higher
molecular weights (Mw ) 2.2 × 104 and Mn ) 2.2 × 104)
than 7a . The better result attained for 7b may be due
to the purity of 3b being higher than that of 3a .
The polymer 2 obtained by the photolysis of 1 was
treated with [W(CO)5(THF)]. The 31P{1H} NMR spec-
trum of the reaction mixture consisted of a broad mul-
tiplet at 0.0 ppm, which is close to that observed for 8.
In addition, another multiplet was observed at 16 ppm.
The results indicated that the polymer prepared from
2 and [W(CO)5(THF)] has lower regularity than 8, pro-
bably because the phosphine sites in 2 act not only as
monodentate sites but also as bi-, tri-, and multidentate
sites.6
Exp er im en ta l Section
Gen er a l Rem a r k s. All reactions were carried out under
an atmosphere of dry nitrogen using Schlenk tube techniques.
All solvents were dried and purified by distillation: CH2Cl2,
1,2-dichloroethane, and CH3CN were distilled from P2O5,
benzene and THF were distilled from sodium/benzophenone,
and hexane was distilled from sodium metal. These purified
solvents were stored under an N2 atmosphere. Other reagents
were used as received. 1 and [W(CO)5(1)] (4) were prepared
according to previously described methods.5a,7a,14
Next, to examine the applicability of the present
photolytic polymerization, the reaction was carried out
with complex 4 and with the free ligand as well. A THF
solution of 4 was irradiated for 10 min in a manner
similar to that above. The 31P{1H} NMR of this solution
consisted of a major singlet at -1.1 ppm with 183W
satellites, J WP ) 249 Hz, and a trace of minor resonaces
at a higher field. The major product was characterized
IR spectra were recorded on a Shimadzu FTIR-8100A
spectrometer. NMR spectra were recorded on a J EOL LA-300
1
as 8 by the IR and H, 13C, and 31P NMR spectra. The
single resonance in 31P{1H} NMR shifted to a field 27.0
ppm higher than that of 4. The three ν(CO) infrared
bands at 2070, 1978, and 1932 cm-1 were almost
identical with those at 2072, 1985, and 1942 cm-1 of 4,
respectively, indicating the presence of the W(CO)5
fragment. The estimated molecular weights of 8 were
as follows: Mw ) 3.0 × 104 and Mn ) 1.8 × 104.
spectrometer. H and 13C NMR chemical shifts were reported
1
relative to Me4Si and were determined by reference to the
residual solvent peaks. 31P NMR chemical shifts were reported
relative to H3PO4 (85%) used as an external reference.
Elemental analyses were performed with a Perkin-Elmer
2400CHN elemental analyzer.
Photolysis was carried out with Pyrex-glass-filtered emis-
sion from a 400 W mercury arc lamp (Riko-Kagaku Sangyo
UVL-400P). The emission lines (nm) used and their relative
intensities (in parentheses) were as follows: 577.0 (69), 546.1
(82), 435.8 (69), 404.7 (42), 365.0 (100), 334.1 (7), 312.6 (38),
and 302.2 (9). Gel permeation chromatography (GPC) analyses
were run on a Shodex GPC-System 11 instrument using a
Shodex KF803L column (exclusion limit 7 × 104) for 7a and
on a Tosoh model SC-8010 using columns of TSKgel G5000H,
G4000H, G3000H, and G2000H (exclusion limits: 4 × 106, 4
Here, it was considered interesting to determine whe-
ther the present photolytic ring-opening reaction re-
quires the coordination of 1 to an organometallic frag-
ment. Thus, the free 1 was irradiated in THF. The 31P-
{1H} NMR spectrum of the products showed a major
singlet at -31.6 ppm with several minor signals. The
chemical shift of the major signal was almost identical
with that reported for the polymer 2 prepared by eq 1.
After sulfurization of the products with elemental
(13) Full details of these structures will be reported elsewhere.
(14) The synthesis of 1 has been previously described. See: (a)
Seyferth, D.; Withers, H. P., J r. J . Organomet. Chem. 1980, 185, C1.
(b) Osborne, A. G.; Whiteley, R. H.; Meads, R. E. J . Organomet. Chem.
1980, 193, 345.
(12) (a) Butler, I. R.; Cullen, W. R.; Einstein, F. W. B.; Rettig, S. J .;
Willis, A. J . Organometallics 1983, 2, 128. (b) Stoeckli-Evans, H.;
Osborne, A. G.; Whiteley, R. H. J . Organomet. Chem. 1980, 194, 91.

5008 Organometallics, Vol. 19, No. 24, 2000
Mizuta et al.
× 105, 6 × 104, and 1 × 104, respectively) for sulsurized 2, 7b,
and 8. The molecular weights were estimated on the basis of
a comparison to polystyrene and poly(methyl methacrylate)
standards for the former and the latter apparatuses, respec-
tively. Preparative-scale GPC was performed with a recycling
HPLC system (J apan Analytical Industry Model LC-908) with
J AIGEL-1H (20 mm i.d. × 600 mm; exclusion limit 1.0 × 103)
and J AIGEL-2H (20 mm i.d. × 600 mm; exclusion limit 5.0 ×
103) columns.
1.1 × 104. Mw/Mn ) 1.96. IR (νCO, cm-1, in THF): 1929, 1864.
1H NMR (δ, in CD2Cl2): 3.91 (d, 2H, Fc), 4.26 (s, 5H, Cp), 4.2-
4.5 (m, 6H, Fc), 7.32 (br, 3H, Ph), 7.63 (br, 2H, Ph). 13C{1H}
NMR (δ, in CD2Cl2): 72.6-75.0 (m, Fc), 83.00 (br, Cp), 84.92
(dm, J PC ) 44.1 Hz, i-Fc), 127.71 (dm, J PC ) 9.3 Hz,Ph), 129.37
(m, Ph), 132.13 (m, Ph), 140.82 (m, i-Ph), 233.30 (dm, J PC
)
24.8 Hz, CO). 31P{1H} NMR (δ, in CDCl3): 73.7.
P r ep a r a tion of 8 by P h otolysis. 4 (194 mg, 0.31 mmol)
and THF (8 mL) were added to a Pyrex Schlenk tube, and the
solution was irradiated for 10 min at 0 °C with the mercury
arc lamp. After a workup similar to that used for 7a , a brown
[Mn (η5-C5H4Me)(CO)2(1)] (3a). [Mn(η5-C5H4Me)(CO)3] (0.50
mL, 0.69 g, 3.16 mmol) and THF (100 mL) were added to a
Pyrex Schlenk tube, and the solution was irradiated with the
400 W mercury arc lamp at 0 °C for 2.5 h. The IR spectra of
the solution indicated that almost half of the initial amount
of the starting tricarbonyl complex remained in the solution,
but further irradiation did not improve the yield of the product
[Mn(η5-C5H4Me)(CO)2(THF)]. To the solution thus obtained
was added 1 (340 mg, 1.16 mmol). After the mixture was
stirred for 7 h, the solvent was removed in vacuo. The residue
was washed three times with hexane (15 mL) and dried in
vacuo to give a reddish brown powder of 3a . Yield: 1.034 g
(89% based on 1). IR (νCO, cm-1, in THF): 1930, 1864. 1H NMR
(δ, in C6D6): 1.68 (s, 3H, Me), 4.00 (m, 4H, Cp′ and Fc), 4.09
(m, 2H, Cp′), 4.16 (m, 2H, Fc), 4.31 (m, 2H, Fc), 5.24 (m, 2H,
Fc), 7.05-7.20 (m, 3H, m- and p-Ph), 7.55-7.70 (m, 2H, o-Ph).
13C{1H} NMR (δ, in C6D6): 13.40 (s, Me), 28.55 (d, J PC ) 15.0
Hz, i-Fc), 76.70 (s, Fc), 76.90 (d, J PC ) 19.8 Hz, Fc), 78.02 (d,
J PC ) 3.7 Hz, Fc), 78.61 (d, J PC ) 8.1 Hz, Fc), 82.06 (s, Cp′),
82.94 (s, Cp′), 98.38 (s, Cp′), 128.78 (d, J PC ) 9.0 Hz, Ph),
129.30 (d, J PC ) 2.9 Hz, p-Ph), 129.41 (d, J PC ) 9.9 Hz, Ph),
140.50 (d, J PC ) 42.2 Hz, i-Ph), 233.04 (d, J PC ) 24.1 Hz, CO).
31P{1H} NMR (δ, in C6D6): 110.5.
powder (155 mg, 80%) was obtained. Mw ) 3.0 × 104. Mn
)
1.8 × 104. Mw/Mn ) 1.71. IR (νCO, cm-1, in THF): 2070, 1978,
1932. 1H NMR (δ, in CDCl3): 3.5-4.8 (br, 8H, Fc), 7.31 (br,
5H, Ph). 13C{1H} NMR (δ, in CDCl3): 72.5-75.5 (m, Fc), 82.5
(m, i-Fc), 128.00 (m, Ph), 129.59 (m, Ph), 130.11 (m, Ph), 138.17
(m, i-Ph), 197.47 (br, CO). 31P{1H} NMR (δ, in THF): -1.10
(J wp ) 249 Hz).
P r ep a r a tion of 2 by P h otolysis. A solution of 1 (495 mg,
1.69 mmol) in THF (40 mL) was irradiated for 10 min at 0 °C
with the mercury arc lamp. A considerable amount of the
resulting precipitates was separated by filtration and dried
in vacuo to give 2a (60 mg). Since the 2a thus obtained was
insoluble in common solvents, characterization by NMR
spectra could not be performed.
The solvent of the filtrate was removed in vacuo to give the
orange residue 2b (477 mg). 31P{1H} NMR (δ, in THF) (relative
intensities are in parentheses): -23.27 (15), -26.33 (25),
-26.78 (5), -29.44 (5), -30.39 (9), -31.56 (100), -35.96 (4),
and -36.87 (10).
Rea ction of 2 w ith Su lfu r . To a suspension of 2a in THF
(10 mL) was added elemental sulfur (30 mg). Though the
suspension was stirred for 2 days, most of the 2a remained as
an unreacted solid. The 31P{1H} NMR spectrum of the super-
natant solution showed signals of a trace of sulfurized products
at 36.4 and 39.6 ppm.
[Mn Cp (CO)2(1)] (3b). 3b was prepared from [MnCp(CO)3]
(400 mg, 1.96 mmol) and 1 (300 mg, 1.02 mmol) in a manner
similar to that used for 3a . 3b (329 mg) thus obtained was
suspended in hexane (100 mL), and CH2Cl2 (17 mL) was added.
After filtration, the solvents of the filtrate were removed in
vacuo, and the residue was dried in vacuo to give a reddish
brown powder of 3b. Yield: 297 mg (62% based on 1). Anal.
Calcd for C23H18FeMnO2P: C, 59.01; H, 3.88. Found: C, 59.24;
H, 4.13. IR (νCO, cm-1, in THF): 1932, 1868. 1H NMR (δ, in
C6D6): 3.98 (br, 2H, Fc), 4.10 (m, 5H, Cp), 4.15 (br, 2H, Fc),
4.30 (br, 2H, Fc), 5.22 (br, 2H, Fc), 7.05-7.20 (m, 3H, m- and
p-Ph), 7.55-7.70 (m, 2H, o-Ph). 13C{1H} NMR (δ, in CD2Cl2):
2b was suspended in CH2Cl2 (15 mL), and elemental sulfur
(200 mg) was added. After the mixture was stirred for 3 h, a
homogeneous solution was obtained and then the solvent was
removed in vacuo. The residue dissolved in CHCl3 was sep-
arated into two fractions by preparative GPC columns. A frac-
tion with higher molecular weight (273 mg after workup) was
examined using analytical GPC columns. Mw ) 1.1 × 104. Mn
) 1.9 × 103. Mw/Mn ) 5.71. 31P{1H} NMR (δ, in CDCl3) (relative
intensities are in parentheses): 38.18 (100) and 31.88 (4).
28.31 (d, J PC ) 16.1 Hz, i-Fc), 76.72 (s, Fc), 76.81 (d, J PC
)
19.2 Hz, Fc), 77.15 (d, J PC ) 4.5 Hz, Fc), 78.49 (d, J PC ) 8.7
Hz, Fc), 82.76 (s, Cp), 129.09 (d, J PC ) 9.3 Hz, Ph), 129.45 (d,
J PC ) 9.3 Hz, Ph), 129.90 (d, J PC ) 2.5 Hz, Ph), 140.01 (d, J PC
) 43.5 Hz, i-Ph), 232.82 (d, J PC ) 24.8 Hz, CO). 31P{1H} NMR
(δ, in C6D6): 110.5.
The other fraction (318 mg after workup) was loaded again
into the preparative GPC column and separated further by a
recycling mode. Five peaks were observed at the first cycle.
After several recyclings, dimeric product 9 was isolated from
the fifth fraction and trimer 10 from the third fraction.
9 (16 mg): 1H NMR (δ, in CDCl3) 4.56 (br, 4H, Fc), 4.67 (br,
8H, Fc), 5.42 (br, 4H, Fc), 7.15-7.30 (m, 6H, Ph), 7.40 (m, 4H,
Ph); 31P{1H} NMR (δ, in CDCl3) 37.66.
10 (40 mg): 1H NMR (δ, in CDCl3) 3.95 (br, 3H, Fc), 4.37
(br, 3H, Fc), 4.68 (br, 3H, Fc), 4.84 (br, 6H, Fc), 5.34 (br, 3H,
Fc), 5.52 (br, 3H, Fc), 5.72 (br, 3H, Fc), 7.41-7.54 (m, 9H, Ph),
7.85 (m, 6H, Ph); 31P{1H} NMR (δ, in CDCl3) 39.13.
P r ep a r a tion of 7a by P h otolysis. 3a (210 mg, 0.436
mmol) and THF (10 mL) were added to a Pyrex Schlenk tube,
and the solution was irradiated for 10 min at 0 °C with the
mercury arc lamp. After filtration to remove a small quantity
of precipitates, the solvent was removed. The residue was
recrystallized from CHCl3/hexane to give a brown powder (211
mg, 90%) as a hemisolvate of CHCl3 per one monomer unit.
Mw ) 3.7 × 103. Mn ) 2.0 × 103. Mw/Mn ) 1.85. Anal. Calcd
for [{C24H20FeMnO2P}‚0.5CHCl3]n: C, 54.31; H, 3.81. Found:
C, 54.51; H, 3.85. IR (νCO, cm-1, in THF): 1926, 1862. 1H NMR
(δ, in CDCl3): 1.91 (br, 3H, Me), 3.6-4.6 (br, 12H, Cp′ and
Fc), 7.2-7.8 (br, 5H, Ph). 13C{1H} NMR (δ, in CDCl3): 13.74
(s, Me), 72.1-74.1 (m, Fc), 81.66 (s, Cp′), 83.21 (s, Cp′), 84.65
(d, J PC ) 43.5 Hz, i-Fc), 98.52 (s, Cp′), 127.25 (br, Ph), 128.83
(br, Ph), 131.65 (br, Ph), 140.61 (d, J PC ) 41.0 Hz, i-Ph), 233.12
(d, J PC ) 23.6 Hz, CO). 31P{1H} NMR (δ, in CDCl3): 74.5.
P r ep a r a tion of 7b by P h otolysis. 3b (250 mg, 0.53 mmol)
and THF (13 mL) were added to a Pyrex Schlenk tube, and
the solution was irradiated for 10 min at 0 °C with the mercury
arc lamp. After a workup similar to that used for 7a , a brown
X-r a y Cr ysta llogr a p h y. Crystal data and refinement
details were as follows: formula C21H13FeO5PW, Mr ) 616.00,
0.60 × 0.35 × 0.25 mm3, a ) 14.3180 (4) Å, b ) 7.1650 (4) Å,
c ) 19.9040 (4) Å, â ) 98.868 (1)°, V ) 2017.51 (7) Å3, Fcalcd
)
2.028 g cm-3, µ ) 65.31 cm-1, Z ) 4, monoclinic, space group
P21/c (No. 14), λ ) 0.710 69 Å, T ) 300 K, R ) 0.040, Rw
)
0.068, GOF ) 1.37, maximum residual positive and negative
electron densities 2.50 and -2.37 e Å-3, respectively, situated
in close proximity to the W atom.
A suitable crystal of 4 was mounted on a glass fiber. All
measurements were made on a Mac Science DIP2030 imaging
plate area detector. The data were collected to a maximum 2θ
powder (186 mg, 74%) was obtained. Mw ) 2.2 × 104. Mn
)

Polymerization of p-Bridged [1]Ferroceneophane
Organometallics, Vol. 19, No. 24, 2000 5009
value of 55.8°. Cell parameters and intensities for the reflection
were estimated using the program packages of MacDENZO.15
A total of 5087 reflections were collected, and 4572 reflections
(I > 3.00σ(I)) were used for the final refinement. The structure
was solved by direct methods and expanded using Fourier
techniques. Non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included but not refined. All calculations
were performed using the teXsan crystallographic software
package from Molecular Structure Corp.16
Sports and Culture of J apan. We thank Dr. Noriyuki
Suzuki (RIKEN, Saitama, J apan) and Dr. Yuushou
Nakayama (Hiroshima University) for performing GPC
measurements. In addition, we are indebted to a re-
viewer for a suggestion concerning the sulfurization of
poly(phenylphosphinoferrocene).
Su p p or tin g In for m a tion Ava ila ble: Tables giving posi-
tional and thermal parameters, crystallographic data, and
bond lengths and angles for 4. This material is available free
of charge via the Internet at http://pubs.acs.org.
Ack n ow led gm en t. This work was supported by
Grants-in-Aid for Science Research (Nos. 11740372 and
12640540) from the Ministry of Education, Science,
OM000453C
(15) Gewirth, D. (with the cooperation of the program authors
Otwinowski, Z.; Minor, W.) MacDENZO. In The MacDenzo Manual-A
Description of the Programs DENZO, XDISPLAYF, and SCALEPACK;
Yale University: New Haven, CT, 1995.
(16) teXsan: Single-Crystal Structure Analysis Software, Version
1.6; Molecular Structure Corp., The Woodlands, TX, 1993.