Metallophosphination of alkynes: Efficient synthesis of β-functionalized alkenylphosphines

Article abstract of DOI:10.1021/om061051t

Reactions of alkynes with [Cp₂Zr(1-butene)(DMAP)] (DMAP = 4-(dimethylamino)pyridine) and chlorophosphines afforded zirconoalkenylphosphines in good to high yields, and their molecular structures were determined by single-crystal X-ray diffracti

Full text of DOI:10.1021/om061051t

1084
Organometallics 2007, 26, 1084-1088
Metallophosphination of Alkynes: Efficient Synthesis of
â-Functionalized Alkenylphosphines
Chanjuan Xi,*,†,‡ Xiaoyu Yan,† and Chunbo Lai†
Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education),
Department of Chemistry, Tsinghua UniVersity, Beijing 100084, People’s Republic of China, and
State Key Laboratory of Elemento-Organic Chemistry, Nankai UniVersity, Tianjin 300071,
People’s Republic of China
ReceiVed NoVember 15, 2006
Reactions of alkynes with [Cp2Zr(1-butene)(DMAP)] (DMAP ) 4-(dimethylamino)pyridine) and
chlorophosphines afforded zirconoalkenylphosphines in good to high yields, and their molecular structures
were determined by single-crystal X-ray diffraction. The zirconoalkenylphosphines could be transformed
into â-functionalized alkenylphosphines through coupling reactions with various electrophiles in the
presence of CuCl.
Introduction
Alkenylphosphines have been attracting interest because they
serve not only as starting materials in organic synthesis1 but
also as useful ligand precursors in organometallic chemistry.2
A number of synthetic methods affording alkenylphosphines
have been reported.3,4 Among them, metal-catalyzed hydro-
phosphination of alkynes, the addition of phosphines to carbon-
carbon triple bonds, provided a straightforward method for the
synthesis of alkenylphosphines.5,6 Nonetheless, it is often
difficult to prepare â-functionalized alkenylphosphines by these
methods. Consequently, development of a versatile and general
method for the preparation of â-functionalized alkenylphos-
phines is a necessity. Herein we report the metallophosphination
of alkynes based on the reaction of alkynes with [Cp2Zr(1-
butene)(DMAP)] (DMAP ) 4-(dimethylamino)pyridine) and
chlorophosphines (eq 1). Moreover, the resulting zirconophos-
phination products 1 can be converted into â-functionalized
alkenylphosphines.
Results and Discussion
We have previously reported that the reaction of alkynes with
Cp2Zr species and chlorophosphates (P(V) compounds) afforded
â-zirconoalkenylphosphonates.7 To achieve the zirconophos-
phination of alkynes, we chose chlorophosphines (P(III) com-
pounds) as reagents. At the outset, to a solution of [Cp2Zr(1-
butene)(DMAP)]8 (1 mmol, generated via Cp2ZrBu2 with
9
DMAP in THF at room temperature) was added 1 equiv of
diphenylacetylene at room temperature. The resulting mixture
was stirred for 1 h. Chlorodiphenylphosphine (1 mmol) then
was added, and stirring was continued for an additional 1 h.
The zirconoalkenylphosphine 1a was mainly observed (eq 2).
* To whom correspondence should be addressed. E-mail: cjxi@
tsinghua.edu.cn.
† Tsinghua University.
‡ Nankai University.
(1) (a) Gilheany, D. G.; Mitchell, C. M. In The Chemistry of Organo-
phosphorus Compounds; Hartley, J. F., Ed.; Wiley: Chichester, U.K., 1990;
Vol. 1, p 151. (b) Brunner, H.; Furst, J. Tetrahedron 1994, 50, 4293.
(2) (a) Adams, H.; Bailey, N. A.; Blenkiron, P.; Morris, M. J. J.
Organomet. Chem. 1993, 460, 73. (b) Hansen, H. D.; Nelson, J. H.
Organometallics 2000, 19, 4740. (c) Glaser, P. B.; Tilley, T. D. Organo-
metallics 2004, 23, 5799. (d) Baya, M.; Buil, M. L.; Esteruelas, M. A.;
On˜ate, E. Organometallics 2005, 24, 2030. (e) Braunstein, P. Chem. ReV.
2006, 106, 134.
(3) (a) Hudson, H. R. In The Chemistry of Organophosphorus Com-
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309-401. (b) Heesche-Wagner, K.; Mitchell, T. N. J. Organomet. Chem.
1994, 468, 99.
1
The H NMR spectrum of 1a showed a singlet at 5.91 ppm
assigned to the Cp protons. In its 13C NMR spectrum, the Cp
carbon signals appeared at 111.2 ppm and two sp2 carbon sig-
nals at 215.0 and 137.8 ppm, assigned to Zr-C(Ph)d and
-C(Ph)dC(Ph)P, respectively. Its 31P NMR spectrum showed
a strong signal at -38.8 ppm, assigned to dC(Ph)PPh2.
Treatment of the reaction mixture with 3 N HCl and extraction
of the product with CH2Cl2 followed by removal of the solvent
afforded 1a as a yellow solid in 90% yield. Further purification
was performed by column chromatography on silica gel (1/1
petroleum ether/THF) to obtain a white powder in 75% isolated
(4) (a) Goldwhite, H. Introduction to Phosphorus Chemistry, Cambridge
University Press: Cambridge, U.K., 1981. (b) Mitchell, T. N.; Heesche,
K. J. Organomet. Chem. 1991, 409, 163.
(5) (a) Douglass, M. R.; Marks, T. J. J. Am. Chem. Soc. 2000, 122, 1824.
(b) Takaki, K.; Koshoji, G.; Komeyama, K.; Takeda, M.; Shishido, T.;
Kitani, A.; Takehira, K. J. Org. Chem. 2003, 68, 6554. (c) Takaki, K.;
Komeyama, K.; Takehira, K. Tetrahedron 2003, 59, 10381.
(6) (a) Arisawa, M.; Yamaguchi, M. J. Am. Chem. Soc. 2000, 122, 2387.
(b) Je´roˆme, F.; Monnier, F.; Lawicka, H.; De´rien, S.; Dixneuf, P. H. Chem.
Commun. 2003, 696. (c) Ohmiya, H.; Yorimitsu, H.; Oshima, K. Angew.
Chem., Int. Ed. 2005, 44, 2368. (d) Alonso, F.; P. Beletskaya, I.; Yus, M.
Chem. ReV. 2004, 104, 3079. (e) Sato, A.; Yorimitsu, H.; Oshima, K. Angew.
Chem., Int. Ed. 2005, 44, 1694.
(7) Lai, C.; Xi, C.; Chen, C.; Ma, M.; Hong, X. Chem. Commun. 2003,
2736.
(8) Wagenen, B. C. V.; Livinghouse, T. Tetrahedron Lett. 1989, 30, 3495.
(9) Negishi, E.; Swanson, D. R.; Cederbaum, F. E.; Takahashi, T.
Tetrahedron Lett. 1986, 27, 2829.
10.1021/om061051t CCC: $37.00 © 2007 American Chemical Society
Publication on Web 01/20/2007

Metallophosphination of Alkynes
Organometallics, Vol. 26, No. 4, 2007 1085
Table 1. Metallophosphination of Alkynes via the Reaction
of Alkynes with [Cp2Zr(1-butene)(DMAP)] and
Chlorophosphines
Figure 1. Molecular structure of 1a. Thermal ellipsoids are shown
at the 30% probability level; hydrogen atoms have been omitted
for clarity. Selected bond lengths (Å) and angles (deg): Zr(1)-
C(3), 2.410(3); Zr(1)-Cl(1), 2.5583(10); Zr(1)-P(1), 2.7458(9);
P(1)-C(2), 1.795(3); C(2)-C(3), 1.364(4); C(3)-Zr(1)-P(1),
57.22(8); C(2)-C(3)-Zr(1), 112.6(2); C(3)-C(2)-P(1), 103.0(2);
C(2)-P(1)-Zr(1), 86.72(11); C(3)-Zr(1)-Cl(1), 130.42(8).
yield. Remarkably, the zirconoalkenylphosphine 1a proved to
be stable to air and water as well as in 3 N HCl solution. It is
worth noting that air- and water-stable C-Zr σ-bond-containing
complexes are rare.10
a NMR yields were obtained in proportion to the integral area of all the
31P signals; isolated yields are given in parentheses. b A mixture of two
regioisomers with a ratio of 2:1; the major isomer is shown.
To confirm the structure of the product, colorless crystals of
1a suitable for X-ray analysis were obtained from its solution
of petroleum ether and THF (15:1) at room temperature. The
structure of 1a in Figure 1 clearly shows the formation of the
zirconophosphination product of diphenylacetylene. The coor-
dination of the phosphorus atom to the zirconium metal center
gives the zirconium atom an 18e electron configuration which
involves two cyclopentadienyl rings, one chlorine atom, one
σ-organyl, and one phosphine. Thus, the air and water stability
may be explained by an electronically saturated (18e) zirconium
center.
Scheme 1
A variety of alkynes were subjected to metallophosphination,
and all reactions afforded analogous products in good to high
yield. The results are summarized in Table 1. When chlorodi-
isopropylphosphine was used instead of chlorodiphenylphos-
phine as phosphination reagent, similar products were obtained
(Table 1, entries 6 and 7). Colorless crystals of 1g suitable for
X-ray analysis were obtained in a manner similar to that for its
analogue 1a, and the structure of 1g is identical with that of
1a, except for the different substituents on the phosphorus atom.
An ORTEP plot of 1g appears in the Supporting Information.
The zirconophosphination products of alkynes are stable in
air, water, and dilute HCl solution. Some of their reactions are
shown in Scheme 1. When 30% H2O2 was added to the THF
solution of complex 1a, compound 2 was produced quantita-
tively. Zr-C to Cu-C transmetalation has been shown to be
an effective method for the activation of Zr-C bonds.11 Thus,
addition of 1 equiv of CuCl to THF solutions of compounds of
type 1 afforded the copper(I) intermediates 3. The intermediates
3 could be converted to â-functionalized, stereodefined alk-
enylphosphines by coupling with electrophiles. Such reactions
of 3a are summarized in Scheme 1. Hydrolysis of 3a with 3 N
HCl gave 4 in 97% NMR yield. Deuteriolysis instead of
hydrolysis of 3a afforded the monodeuterated compound 5 in
95% yield with 93% deuterium incorporation. It is noteworthy
that in compounds 4 and 5 phosphine-CuCl complexes are
formed. The formation of 5 provides good proof that the Zr-C
bond has been replaced by the more active Cu-C bond. It is
well-known that the diethyldithiocarbamate ligand possesses the
unsuspected capacity of effectively stabilizing transition met-
als.12 To remove Cu(I) from the products, 3a was treated with
water followed by 2.2 equiv of sodium diethyldithiocarbamate;
(10) (a) Luker, T.; Whitby, R. J.; Webster, M. J. Organomet. Chem.
1995, 492, 53. (b) Mohamadi, F.; Spees, M. M. Organometallics 1992, 11,
1398. (c) Takahashi, T.; Xi, C.; Xi, Z.; Kageyama, M.; Fischer, R.;
Nakajima, K.; Negishi, E. J. Org. Chem. 1998, 63, 6802. (d) Zhou, S.; Liu,
D.; Liu, Y. Organometallics 2004, 23, 5900.
(11) (a) Takahashi, T.; Kotora, M.; Kasai, K.; Suzuki, N.; Nakajima, N.
Organometallics 1994, 13, 4183. (b) Takahashi, T.; Hara, R.; Nishihara,
Y.; Kotora, M. J. Am. Chem. Soc. 1996, 118, 5154. (c) Xi, C.; Kotora, M.;
Nakajima, K.; Takahashi, T. J. Org. Chem. 2000, 65, 945.

1086 Organometallics, Vol. 26, No. 4, 2007
Xi et al.
Scheme 2
pressure. The reaction progress was monitored by 31P NMR. The
31P NMR yields were obtained in proportion to the integral area of
all the 31P signals determined by integration of all the 31P signals.
Zirconocene dichloride, n-BuLi (1.6 M solution in hexane), and
DMAP were purchased from Aldrich Chemical Co. Inc. Chloro-
diphenylphosphine, chlorodiisopropylphosphine, and alkynes were
purchased from Fluka Co. Inc. Unless otherwise noted, all starting
materials were used without further purification. Tetrahydrofuran
(THF) was refluxed and freshly distilled from dark purple solutions
of sodium and benzophenone under a nitrogen atmosphere. 1H NMR
and 13C NMR spectra were recorded on a JEOL 300 NMR
spectrometer with TMS as internal standard. 31P NMR spectra were
recorded on a Bruker AC 200 NMR spectrometer at 81 MHz using
85% H3PO4 (δP 0) as an external standard. Mass spectra were
obtained using a Bruker Esquire ion trap mass spectrometer in the
positive ion mode. Elemental analyses were performed on a Flash
EA 1112 instrument.
Typical Procedure for the Reaction of [Cp2Zr(R1CtCR2)-
(DMAP)] with Chlorodiphenylphosphine: Preparation of (Z)-
[2-(Dicyclopentadienylchlorozircono)-1,2-diphenylvinyl]diphen-
ylphosphine (1a). To a solution of Cp2ZrCl2 (1.2 mmol, 351 mg)
in 5 mL of THF was added n-BuLi (2.4 mmol, 1.5 mL, 1.6 M in
hexane) at -78 °C, and the mixture was stirred for 1 h at the same
temperature. To this solution was added 366 mg of 4-(dimethyl-
amino)pyridine (DMAP, 3.0 mmol). The resulting mixture was
warmed to room temperature and stirred for 1 h. Diphenylacetylene
(1.0 mmol, 178 mg) was added, and the mixture was stirred for 1
h at the same temperature. Subsequently PPh2Cl (184 µL, 1.0 mmol)
was added, and the solution was stirred for 1 h at room temperature.
31P NMR (81 MHz, THF, 85% H3PO4): δ -38.8. The NMR yield
is 95%. The solvents were evaporated under reduced pressure. The
resulting residue was washed with 3 N HCl. Extraction of the
product with CH2Cl2 and removal of the solvent afforded 1a as a
yellow solid in 90% yield. Further purification was performed by
column chromatography on silica gel (1/1 petroleum ether/THF)
to obtain a white powder (464 mg, 75% isolated yield). Mp: 227-
compound 6 was formed in 95% NMR yield and in 71% isolated
yield after purification by short-column chloromatography. The
reaction of 3a with allyl bromide gave the corresponding
products 7 and 8 after treatment with Et2NCS2Na‚3H2O and
H2O2, respectively. Treatment of 3a with 3 equiv of iodine gave
the product 9 after hydrolysis. It is worth noting that direct
iodination of 1a led to the formation of a complex mixture.
Only a trace amount of 9 was detected by GC-MS after
hydrolysis.
Coupling reactions of zirconocene alkyne complexes with
various unsaturated compounds such as alkynes, alkenes, and
ketones have been reported.8,9,13 Although the mechanism of
reaction presented here is not yet clear, one possible reaction
pathway is shown in Scheme 2. Reaction of [Cp2Zr(1-butene)-
(DMAP)] with alkynes gives the zircono-alkyne complex 10
or the zirconacyclopropene 11.8,9,13 Complex 10 or 11 reacts
with ClPR2 to give product 1 via complex 12 or 13. An
alternative reaction pathway involving oxidative addition of
ClPR2 to the complex [Cp2Zr(R1CCR2)(DMAP)], giving [Cp2-
ClZrPR2(R1CCR2)(DMAP)], and subsequent insertion of alkynes
into the Zr-PR2 moiety to afford 1 cannot be ruled out.14
In conclusion, zirconophosphination of alkynes to produce
air- and water-stable phosphazirconacyclobutene has been
described. The resulting zirconoalkenylphosphines, as character-
ized by X-ray crystal analysis, can act as useful intermediates
for the construction of various â-functionalized alkenylphos-
phosphine derivatives.
1
228 °C. H NMR (300 MHz, CDCl3, Me4Si): δ 5.91 (s, 10H),
6.81-6.84 (m, 2H), 6.96-7.12 (m, 6H), 7.26-7.31 (m, 2H),7.40-
7.42 (m, 6H), 7.73-7.79 (m, 4H). 13C NMR (75 MHz, CDCl3,
Me4Si): δ 111.2, 124.9, 125.0, 126.3, 127.8, 128.5, 128.7 (d, 3JPC
3
2
) 7.5 Hz), 129.1 (d, JPC ) 3.0 Hz), 129.7, 132.8 (d, JPC ) 9.8
1
1
Hz), 133.2 (d, JPC ) 18.6 Hz), 137.8 (d, JPC ) 38.7 Hz), 138.0
2
3
2
(d, JPC ) 2.9 Hz), 150.4 (d, JPC ) 38.7 Hz), 215.0 (d, JPC
)
21.5 Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4) δ -40.0.
Positive ion ESI-MS: 583.0 (M - Cl). Anal. Calcd for C36H30-
ClPZr: C, 69.71; H, 4.87. Found: C, 69.66; H, 4.79.
(Z)-[2-(Dicyclopentadienylchlorozircono)-1,2-dipropylvinyl]-
diphenylphosphine (1b). White solid (326 mg, 63%). Mp: 167-
1
3
168 °C. H NMR (300 MHz, CDCl3, Me4Si): δ 0.73 (t, JHH
)
3
7.2 Hz, 3H), 0. 85 (m, 2H), 1.07 (t, JHH ) 7.5 Hz, 3H), 1.66-
1.74 (m, 2H), 2.26-2.40 (m, 4H), 5.90 (s, 10H), 7.37 (m, 6H),
7.56-7.62 (m, 4H). 13C NMR (75 MHz, CDCl3, Me4Si): δ 14.5,
15.7, 22.4, 24.0, 34.0 (d, 2JPC ) 3.6 Hz), 42.4 (d, 3JPC ) 37.3 Hz),
110.1, 128.5 (d, 3JPC ) 7.9 Hz), 129.4, 133.3 (d, 2JPC ) 10.5 Hz),
135.0 (d, JPC ) 18.6 Hz), 138.8 (d, JPC ) 40.2 Hz), 214.1 (d,
2JPC ) 15.1 Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ
-44.2. Positive ion ESI-MS: 515.0 (M - Cl). Anal. Calcd for
C30H34ClPZr: C, 65.25; H, 6.21. Found: C, 65.35; H, 6.24.
Experimental Section
General Comments. All manipulations were conducted in
predried Schlenk tubes and under nitrogen with a slightly positive
1
1
(12) (a) Hendrickson, A. R.; Martin, R. L.; Rohde, N. M. Inorg. Chem.
1974, 13, 1933. (b) Chant, R.; Hendrickson, A. R.; Martin, R. L.; Rohde,
N. M. Inorg. Chem. 1975, 14, 1894. (c) Hendrickson, A. R.; Martin, R. L.;
Rohde, N. M. Inorg. Chem. 1975, 14. 2980. (d) Brinkhoff, H. C.; Cras, J.
A.; Steggerda, J. J.; Willemse, J. Recl. Trau. Chim. Pays-Bas 1969, 88,
633.
(13) (a) Erker, G.; Dorf, U.; Mynott. R.; Tsay, Y.-H.; Kru¨ger, C. Angew.
Chem., Int. Ed. Engl. 1985, 24, 584. (b) Buchwald, S. L.; Watson, B. T. J.
Am. Chem. Soc. 1987, 109, 2544. (c) Takahashi, T.; Suzuki, N.; Kaheyama,
M.; Kondakov. D. Y.; Hara, R. Tetrahedron Lett. 1993, 34, 4811.
(14) (a) Hey-Hawkins, E.; Lindenberg, F. Chem. Ber. 1992, 125, 1815.
(b) Matthias, W.; Matthias, H. D.; Heinrich, N.; Thomas, S.; Arno, P. J.
Am. Chem. Soc. 1998, 120, 6722.
(Z)-[2-(Dicyclopentadienylchlorozircono)-1,2-di-n-butylvinyl]-
diphenylphosphine (1c). White solid (377 mg, 65%). Mp: 183-
1
3
184 °C. H NMR (300 MHz, CDCl3, Me4Si): δ 0.72 (t, JHH
)
7.2 Hz, 3H), 1.03 (t, 3JHH ) 7.2 Hz, 3H), 1.11-1.18 (m, 2H), 1.28-
1.35 (m, 2H), 1.43-1.51 (m, 2H), 1.62-1.72 (m, 2H), 2.28-2.42
(m, 4H), 5.90 (s, 10H), 7.37 (m, 6H), 7.56-7.62 (m, 4H). 13C NMR
(75 MHz, CDCl3, Me4Si): δ 13.8, 14.2, 23.0, 24.2, 31.1, 31.4 (d,
2JPC ) 3.6 Hz), 32.8, 39.6 (d, JPC ) 37.3 Hz), 110.1, 128.4 (d,
3
3JPC ) 7.9 Hz), 129.4, 133.3 (d, 2JPC ) 10.8 Hz), 135.0 (d, 1JPC
)

Metallophosphination of Alkynes
Organometallics, Vol. 26, No. 4, 2007 1087
17.9 Hz), 138.8 (d, 1JPC ) 38.7 Hz), 214.1 (d, 2JPC ) 15.1 Hz). 31
NMR (81 MHz, CDCl3, 85% H3PO4): δ -44.2. Positive ion ESI-
MS: 543.0 (M - Cl). Anal. Calcd for C32H38ClPZr: C, 66.23; H,
6.60. Found: C, 66.23; H, 6.66.
P
31P NMR (81 MHz, CDCl3, 85% H3PO4): δ 29.9. Positive ion ESI-
1
MS: 381.1 (M + H+), 403.1 (M + Na+). H and 13C NMR data
are consistent with the published data.5c
{[(E)-(1,2-Diphenylvinyl)diphenylphosphine)]CuCl} (4). To
a solution of 1a (0.4 mmol, 248 mg) in 5 mL of THF were added
40 mg of CuCl (0.4 mmol) and 5 µL of H2O, and the solution was
stirred for 2 h at 50 °C. 31P NMR (81 MHz, THF, 85% H3PO4):
δ 13.2. The NMR yield was 97%. Removal of the solvent and
subsequent purification by column chromatography on silica gel
(1/1 ethyl acetate/ petroleum ether) afforded 126 mg of the title
compound as a yellow solid (isolated yield 65%). Mp: 89-90 °C.
1H NMR (300 MHz, CDCl3, Me4Si): δ 4.1 (br, H2O), 6.94-7.66
(m, 21H). 13C NMR (75 MHz, CDCl3, Me4Si): δ 127.6, 128.2,
(Z)-[2-(Dicyclopentadienylchlorozircono)-1,2-bis(4-methylphen-
yl)vinyl]diphenylphosphine (1d). White solid (473 mg, 73%).
1
Mp: 230-231 °C. H NMR (300 MHz, CDCl3, Me4Si): δ 2.18
(s, 3H), 2.34 (s, 3H), 5.89 (s, 10H), 6.73-6.79 (m, 4H), 6.92-
6.95 (m, 2H), 7.09-7.11 (m, 2H),7.40-7.42 (m, 6H), 7.76-7.78
(m, 4H). 13C NMR (75 MHz, CDCl3, Me4Si): δ 21.2, 111.1, 124.9,
3
3
128.5, 128.6 (d, JPC ) 7.9 Hz), 129.0 (d, JPC ) 2.9 Hz), 129.2,
4
2
129.60 (d, JPC ) 1.4 Hz), 132.7 (d, JPC ) 10.0 Hz), 133.2 (d,
1JPC ) 17.9 Hz), 134.2, 135.1 (d, 2JPC ) 2.9 Hz), 135.8, 137.3 (d,
1JPC ) 40.2 Hz), 147.6 (d, JPC ) 40.2 Hz), 214.5 (d, JPC ) 20.1
Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ -41.0. Positive
ion ESI-MS: 611.0 (M - Cl). Anal. Calcd for C38H34ClPZr: C,
70.40; H, 5.29. Found: C, 70.51; H, 5.30.
3
2
3
4
128.3, 128.8 (d, JPC ) 9.3 Hz), 128.8, 130.2 (d, JPC ) 4.3 Hz),
130.2, 130.4, 131.9 (d, 1JPC ) 33.0 Hz), 135.0 (d, 2JPC ) 15.8 Hz),
1
3
136.5 (d, JPC ) 26.3 Hz), 136.6 (d, JPC ) 15.8 Hz), 138.6 (d,
2JPC ) 8.6 Hz), 143.0 (d, JPC ) 22.9 Hz). 31P NMR (81 MHz,
2
CDCl3, 85% H3PO4): δ 12.5. Positive ion ESI-MS: 427.1 (M -
Cl). Anal. Calcd for C26H21ClCuP‚H2O: C, 64.86; H, 4.82.
Found: C, 64.51; H, 4.61.
(Z)-[2-(Dicyclopentadienylchlorozircono)-2-ethyl-1-phenylvi-
1
nyl]diphenylphosphine (1e). H NMR (300 MHz, CDCl3, Me4-
Si): δ 0.98 (t, J ) 7.2 Hz, 3H), 2.60 (m, J ) 3.78 Hz, 4JPH ) 15.1
Hz, 2H), 6.00 (s, 10H), 7.08-7.11 (m, 2H), 7.20-7.23 (m, 3H),
7.32-7.34 (m, 6H), 7.57-7.62 (m, 4H). 13C NMR (75 MHz,
{[(E)-(2-Deuterio-1,2-diphenylvinyl)diphenylphosphine]-
1
CuCl} (5). H NMR (300 MHz, CDCl3, Me4Si): δ 4.4 (br, H2O)
3
6.87-7.55 (m, 20H). 13C NMR (75 MHz, CDCl3, Me4Si): δ 127.4,
CDCl3, Me4Si): δ 14.4, 32.4 (d, JPC ) 35.9 Hz), 110.1, 126.5,
3
3
128.1, 128.2, 128.6 (d, 3JPC ) 12.9 Hz), 128.7, 129.6, 129.9, 130.0,
128.0 (d, JPC ) 2.2 Hz), 128.4 (d, JPC ) 7.9 Hz), 128.4, 129.5,
133.3 (d, 2JPC ) 10.0 Hz, 4C), 134.2 (d, 1JPC ) 17.9 Hz), 138.3 (d,
1
2
130.8 (d, JPC ) 34.4 Hz), 134.5 (d, JPC ) 14.3 Hz), 135.3 (d,
1JPC ) 39.4 Hz), 139.9 (d, JPC ) 3.6 Hz), 220.3 (d, JPC ) 16.5
Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ -39.4. Positive
ion ESI-MS: 535.0 (M - Cl). Anal. Calcd for C32H30ClPZr: C,
67.17; H, 5.28. Found: C, 67.01; H, 5.15.
2
2
1JPC ) 26.5 Hz), 135.9 (d, JPC ) 13.6 Hz), 138.2 (d, JPC ) 8.6
Hz), 142.9 (m). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ 13.0.
Positive ion ESI-MS: 427.9 (M - Cl). Anal. Calcd for C26H20-
DClCuP‚H2O: C, 64.73; H, 5.01. Found: C, 64.49; H, 4.98.
3
2
(Z)-[2-(Dicyclopentadienylchlorozircono)-1-ethyl-2-phenylvi-
(E)-(1,2-Diphenylvinyl)diphenylphosphine (6). To a solution
of 3a prepared in situ by 1a (0.1 mmol, 62 mg) and CuCl (0.1
mmol, 10 mg) in 1 mL of THF was added 2 µL of H2O, followed
by addition of sodium diethyldithiocarbamate trihydrate (50 mg,
0.22 mmol). After the mixture had been stirred for 2 h at room
temperature, removal of the solvent and subsequent purification
by column chromatography on silica gel (1/25 ethyl acetate/
petroleum ether) afforded 26 mg of the title compound as a white
solid (isolated yield 71%). 1H NMR (300 MHz, CDCl3, Me4Si): δ
1
nyl]diphenylphosphine (1e′). H NMR (300 MHz, CDCl3, Me4-
3
Si): δ 0.63 (t, J ) 7.5 Hz, 3H), 2.22-2.29 (m, J ) 7.5 Hz, JPH
) 2.4 Hz, 2H), 5.91 (s, 10H), 7.16-7.26 (m, 2H), 7.34-7.38 (m,
3H), 7.41-7.45 (m, 6H), 7.69-7.75 (m, 4H). 13C NMR (75 MHz,
CDCl3, Me4Si): δ 14.8, 25.7 (d, 2JPC ) 4.3 Hz), 111.1, 123.9, 124.5,
125.6, 128.7 (d, 3JPC ) 8.6 Hz), 129.7, 133.1 (d, 2JPC ) 10.8 Hz),
1
1
134.1 (d, JPC ) 18.6 Hz), 141.2 (d, JPC ) 37.3 Hz), 150.5 (d,
3JPC ) 39.4 Hz), 221.2 (d, JPC ) 24.4 Hz). 31P NMR (81 MHz,
2
3
CDCl3, 85% H3PO4): δ -40.2. Positive ion ESI-MS: 535.0
(M -Cl).
(Z)-[2-(Dicyclopentadienylchlorozircono)-1,2-diphenylvinyl]-
diisopropylphosphine (1g). White solid (392 mg, 71%). Mp: 226-
227 °C. 1H NMR (300 MHz, CDCl3, Me4Si): δ 1.25 (dd, J ) 7.2
6.57 (d, JPH ) 9.2 Hz, 1H), 6.93-7.00 (m, 2H), 7.09-7.25 (m,
8H), 7.33-7.40 (m, 6H), 7.48-7.52 (m, 4H). 13C NMR (75 MHz,
CDCl3, Me4Si): δ 127.1, 127.4, 128.1, 128.5, 128.6 (d, 3JPC ) 5.0
Hz), 129.1, 129.3 (d, 4JPC ) 6.5 Hz), 129.5, 134.4 (d, 2JPC ) 19.4
Hz), 135.5 (d, 1JPC ) 11.5 Hz), 137.0 (d, 2JPC ) 6.5 Hz), 138.2 (d,
2JPC ) 18.6 Hz), 140.1 (d, 1JPC ) 16.5 Hz), 141.6 (d, 3JPC ) 18.6
Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ 9.1. Positive ion
ESI-MS: 365.2 (M + H+), 387.1 (M + Na+). Spectroscopic
characterization data for compound 6 are consistent with the
published data.5b
3
3
Hz, JPH ) 12.4 Hz, 6H), 1.48 (dd, J ) 7.2 Hz, JPH ) 14.8 Hz,
6H), 2.51 (m, J ) 7.2 Hz, 2JPH ) 3.1 Hz, 2H), 6.08 (s, 10H), 6.85-
7.13 (m, 10H). 13C NMR (75 MHz, CDCl3, Me4Si): δ 19.9, 20.8
2
1
(d, JPC ) 5.7 Hz), 26.7 (d, JPC ) 2.9 Hz), 110.5, 124.2, 125.2,
2
1
125.9, 127.9, 128.3, 140.8 (d, JPC ) 2.2 Hz), 140.9 (d, JPC
)
3
2
33.0 Hz), 150.6 (d, JPC ) 34.4 Hz, 1C), 209.6 (d, JPC ) 23.7
Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ -24.6. Positive
ion ESI-MS: 515.1 (M - Cl). Anal. Calcd for C30H34ClPZr: C,
65.25; H, 6.21. Found: C, 65.15; H, 6.33.
Preparation of (E)-(1,2-Diphenylpenta-1,4-dienyl)diphenyl-
phosphine (7). To a solution of 1a (0.4 mmol, 248 mg) in 5 mL
of THF were added 40 mg of CuCl (0.4 mmol) and 35 µL of allyl
bromide (0.4 mmol), and the solution was stirred for 2 h at 50 °C.
Sodium diethyldithiocarbamate trihydrate (200 mg, 0.88 mmol) was
added. After the mixture had been stirred for 2 h at room
temperature, removal of the solvent and subsequent purification
by column chromatography on silica gel (1/25 ethyl acetate/
(Z)-[2-(Dicyclopentadienylchlorozircono)-1,2-dibutylvinyl]di-
1
isopropylphosphine (1h). Oily liquid (353 mg, 69%). H NMR
(300 MHz, CDCl3, Me4Si): δ 0.93 (t, J ) 6.8 Hz, 3H), 0. 96 (t, J
) 7.2 Hz, 3H), 1.14-1.50 (m, 20H), 2.01-2.10 (m, 2H), 2.14-
2.33 (m, 4H), 6.00 (s, 10H). 13C NMR (75 MHz, CDCl3, Me4Si):
1
petroleum ether) afforded the title compound (210 mg, 52%). H
2
NMR (300 MHz, CDCl3, Me4Si): δ 3.98 (d, 3JHH ) 6.2 Hz, 2H),
5.04 (d, 3JHH(cis) ) 11.3 Hz, 1H), 5.09 (d, 3JHH(trans) ) 17.2 Hz,
1H), 5.85 (m), 6.75-7.78 (m, 20H). 13C NMR (75 MHz, CDCl3,
δ 14.0, 14.2, 20.4, 20.8 (d, JPC ) 5.7 Hz), 23.6, 24.2, 25.9 (d,
4
3
1JPC ) 2.2 Hz), 31.5, 32.0 (d, JPC ) 3.6 Hz), 32.4 (d, JPC ) 5.0
3
1
Hz), 38.9 (d, JPC ) 33.0 Hz), 109.6 (10C), 140.5 (d, JPC ) 34.4
Hz), 209.4 (d, JPC ) 14.1 Hz). 31P NMR (81 MHz, CDCl3, 85%
2
3
Me4Si): δ 41.3 (d, JPC ) 30.1 Hz), 117.0, 125.3, 126.5, 126.9
(2C), 127.6 (2C), 128.2 (d, 3JPC ) 5.7 Hz, 4C), 128.3 (2C), 128.8
H3PO4): δ -30.9. Positive ion ESI-MS: 475.0 (M - Cl). Anal.
Calcd for C26H42ClPZr: C, 60.90; H, 8.26. Found: C, 60.98;
H, 8.35.
Reaction of [(Z)-2-(Dicyclopentadienylchlorozircono)-1,2-
diphenylvinyl]diphenylphosphine (1a). (E)-(1,2-Diphenylvinyl)-
diphenylphosphine Oxide (2). White solid, 79% isolated yield.
4
2
(d, JPC ) 5.0 Hz, 2C), 129.1 (2C), 129.9, 133.8 (d, JPC ) 20.1
2
1
Hz, 4C), 135.2, 136.4 (d, JPC ) 20.1 Hz), 136.8 (d, JPC ) 12.2
Hz, 2C), 137.2 (d, 1JPC ) 22.2 Hz), 140.2 (d, 2JPC ) 5.0 Hz), 142.3
3
(d, JPC ) 6.5 Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ
-4.8. Positive ion ESI-MS: 405.2 (M + H+). HRMS: calcd for

1088 Organometallics, Vol. 26, No. 4, 2007
Xi et al.
3
2
Table 2. Crystal Data
1a
134.6 (d, JPC ) 11.5 Hz), 138.5 (d, JPC ) 11.5 Hz), 143.3 (d,
2JPC ) 14.3 Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ 26.2.
Positive ion ESI-MS: 421.2 (M + H+), 443.1 (M + Na+).
HRMS: calcd for C29H25OP, 420.1643; found, 420.1650. Anal.
Calcd for C29H25OP: C, 82.84; H, 5.99. Found: C, 82.69; H, 6.08.
Preparation of (Z)-(2-Iodo-1,2-diphenylvinyl)diphenylphos-
phine Oxide (9). To a solution of 1a (0.1 mmol, 62 mg) in 2 mL
of THF were added 38 mg of CuI (0.2 mmol) and 76 mg of I2 (0.3
mmol), and the solution was stirred for 2 h at 50 °C. 31P NMR (81
MHz, THF, 85% H3PO4): δ 54.8. The reaction mixture was treated
with Na2S2O3. Removal of the solvent and subsequent purification
by column chromatography on silica gel (2/1 ethyl acetate/petroleum
1g
empirical formula
formula wt
cryst color
temp (K)
Crystal system
space group
a (Å)
C36H30ClPZr
620.24
colorless
293(2)
monoclinic
P21/c
19.0266(9)
8.3521(4)
19.7203(9)
110.936(3)
2926.9(2)
4
1.408
0.545
1272
0.24 × 0.18 × 0.12
2.10-28.31
-25 e h e 25,
-8 e k e 11,
-26 e l e 21
26 546
C30H34ClPZr
552.21
colorless
298(2)
monoclinic
P21/c
13.8113(1)
12.0911(9)
16.0607(1)
91.971(3)
2680.5(4)
4
b (Å)
c (Å)
â (deg)
V (Å3)
1
Z
D
ether) afforded the title compound (23 mg, 45%). H NMR (300
calcd (g cm-3
)
1.368
0.586
1144
MHz, CDCl3, Me4Si): δ 6.71-7.73 (m, 20H). 13C NMR (75 MHz,
µ (mm-1
F(000)
)
2
CDCl3, Me4Si): δ 117.2 (d, JPC ) 4.3 Hz), 126.7, 127.7, 128.0,
3
128.3 (4C), 128.3 (d, JPC ) 12.2 Hz, 4C), 128.4 (2C), 139.8 (d,
cryst size (mm)
θ range (deg)
limiting indices
0.43 × 0.22 × 0.20
2.11-28.30
-18 e h e 15,
-16 e k e 16,
-21 e l e 16
24 933
3JPC ) 3.6 Hz, 2C), 131.5 (d, 4JPC ) 2.5 Hz, 2C), 132.0 (d, 2JPC
)
9.3 Hz, 4C), 132.3 (d, 1JPC ) 107.5 Hz, 2C), 138.7 (d, 3JPC ) 10.8
Hz), 145.2 (d, JPC ) 38.06 Hz), 145.3 (d, JPC ) 53.1 Hz). 31P
NMR (81 MHz, CDCl3, 85% H3PO4): δ 30.9. Positive ion ESI-
MS: 507.0 (M + H+). HRMS: calcd for C26H20IOP, 506.0296;
found, 506.0290. Anal. Calcd for C26H20IOP: C, 61.68; H,3.98.
Found: C, 61.59; H, 4.09.
2
1
no. of rflns collected
no. of unique rflns
completeness to θ (%)
abs cor
7227
6614
99.3 (θ ) 28.31°)
empirical
352
99.4 (θ ) 28.30°)
empirical
302
X-ray Crystallographic Studies. Single-crystal X-ray diffraction
studies for 1a and 1g were carried out on a Bruker SMART 1000
CCD diffractometer with graphite-monochromated Mo KR radiation
(λ ) 0.710 73 Å). Cell parameters were obtained by global
refinement of the positions of all collected reflections. Intensities
were corrected for Lorentz and polarization effects and empirical
absorption. The structures were solved by direct methods and
refined by full-matrix least squares on F2. All non-hydrogen atoms
were refined anisotropically. All hydrogen atoms were placed in
calculated positions. Structure solution and refinement were
performed by using the SHELXL-97 package.15 Crystal data and
processing parameters for 1a and 1g are summarized in Table 2.
no. of params
goodness of fit on F2
final R indices (I > 2σ(I))
0.919
0.812
R1 ) 0.0479,
wR2 ) 0.0606
R1 ) 0.1681,
wR2 ) 0.0730
0.437, -0.823
R1 ) 0.0486,
wR2 ) 0.0769
R1 ) 0.1997,
wR2 ) 0.0978
0.374, -0.802
R indices (all data)
largest diff peak,
hole (e Å-3
)
C29H25P, 404.1694, found 404.1699. Anal. Calcd for C29H25P: C,
86.11; H, 6.23. Found: C, 86.01; H, 6.33.
(E)-(1,2-Diphenylpenta-1,4-dienyl)diphenylphosphine Oxide
(8). To a solution of 1a (0.4 mmol, 248 mg) in 5 mL of THF were
added 40 mg of CuCl (0.4 mmol) and 35 µL of allyl bromide (0.4
mmol), and the solution was stirred for 2 h at 50 °C. Then 30%
H2O2 (2 mL) was added dropwise and the mixture was stirred for
24 h. 31P NMR (81 MHz, THF, 85% H3PO4): δ 26.9. The NMR
yield was 76%. Removal of the solvent and subsequent purification
by column chromatography on silica gel (2/1 ethyl acetate/petroleum
Acknowledgment. This work has been supported by the
National Natural Science Foundation of China (Grant No.
20372041). We thank Prof. Wen-Hua Sun, Dr. Katrin Wedeking,
and Mr. Peng Hao for the single-crystal X-ray analysis. Prof.
Dietmar Seyferth is gratefully acknowledged for his kind
editorial and English corrections.
1
ether) afforded the title compound as an oil (214 mg, 51%). H
NMR (300 MHz, CDCl3, Me4Si): δ 3.76 (d, J ) 6.5 Hz, 2H),
Supporting Information Available: X-ray crystallography data
as CIF files for complexes 1a and 1g and an ORTEP plot of 1g.
This material is available free of charge via the Internet at
http://pubs.acs.org.
4.70 (d, 3JHH(trans) ) 16.8 Hz, 1H), 4.74 (d, 3JHH(cis) ) 10.3 Hz,
3
3
1H), 5.49 (dd, JHH(trans) ) 16.8 Hz, JHH(cis) ) 10.3 Hz, 1H),
6.90-7.05 (m, 6H), 7.22-7.39 (m, 10H), 7.54-7.77 (m, 4H). 13
C
NMR (75 MHz, CDCl3, Me4Si): δ 41.5 (d, 3JPC ) 7.9 Hz), 117.6,
126.1, 127.0, 127.6 (d, 3JPC ) 15.8 Hz), 128.2, 128.4, 128.4, 131.0
OM061051T
3
4
2
(d, JPC ) 3.6 Hz), 131.4 (d, JPC ) 2.2 Hz), 131.9 (d, JPC ) 9.3
Hz), 132.9 (d, 1JPC ) 50.2 Hz), 133.9 (d, 1JPC ) 101.8 Hz), 134.0,
(15) Sheldrick, G. M. SHELXTL-97, Program for the Refinement of
Crystal Structures; University of Go¨ttingen, Go¨ttingen, Germany, 1997.