Generation of copper(I) complexes with a tethered olefin-phosphine ligand from CuCl-mediated reaction of alkenylzirconocene with R2PCl

Article abstract of DOI:10.1021/om000592u

α-substituted alkenylzirconocenes, Cp₂Zr(OSiMe₃){C(R)=C(R)CH₂CH=CH₂} (R = Pr (1a); R = Ph (1c)), which were prepared in situ by the reaction of zirconacyclopentenes with (allyloxy)trimethylsilane, reacted with R′₂PCl in the presence of CuCl to give the Cu(I) complexes [(μ-Cl)Cu(PR′₂C(R)=C (R)CH₂CH=CH₂)]₂ (R = Pr, R′ = Ph (2a); R = Pr, R′ = i-Pr (2b); R = Ph, R′ = i-Pr (2c)) with tethered olefin-phosphine ligands bidentately coordinating to copper(I) in good to high yields. The molecular structures of 2a and 2c were determined by single-crystal X-ray diffraction studies.

Full text of DOI:10.1021/om000592u

Organometallics 2001, 20, 2859-2863
2859
Gen er a tion of Cop p er (I) Com p lexes w ith a Teth er ed
Olefin -P h osp h in e Liga n d fr om Cu Cl-Med ia ted Rea ction
of Alk en ylzir con ocen e w ith R2P Cl
Taichi Miyaji,† Zhenfeng Xi,‡ Kiyohiko Nakajima,§ and Tamotsu Takahashi*,†
Catalysis Research Center and Graduate School of Pharmaceutical Sciences,
Hokkaido University, and CREST, Science and Technology Corporation (J ST),
Sapporo 060-0811, J apan, and Peking University-Hokkaido University J oint Laboratory,
Department of Chemistry, Peking University, Beijing 100871, China, and Department of
Chemistry, Aichi University of Education, Igaya, Kariya 448-8542, J apan
Received J uly 11, 2000
R-Substituted alkenylzirconocenes, Cp2Zr(OSiMe3){C(R)dC(R)CH2CHdCH2} (R ) Pr (1a );
R ) Ph (1c)), which were prepared in situ by the reaction of zirconacyclopentenes with
(allyloxy)trimethylsilane, reacted with R′2PCl in the presence of CuCl to give the Cu(I)
complexes [(µ-Cl)Cu(PR′2C(R)dC(R)CH2CHdCH2)]2 (R ) Pr, R′ ) Ph (2a ); R ) Pr, R′ ) i-Pr
(2b); R ) Ph, R′ ) i-Pr (2c)) with tethered olefin-phosphine ligands bidentately coordinating
to copper(I) in good to high yields. The molecular structures of 2a and 2c were determined
by single-crystal X-ray diffraction studies.
Sch em e 1
In tr od u ction
Phosphine compounds have been widely used as
ligands in coordination chemistry and transition-metal
catalysts. We have investigated the preparative methods
for phosphine compounds from organozirconocene com-
plexes.1 Zirconacyclopentanes and zirconacyclopentenes
reacted with Ph2PCl to form alkylphosphine and homo-
allylphosphine compounds, respectively.2 These phos-
phine compounds were formed by a selective reaction
of the Zr-C(sp3) bonds. It is known that reactions of
zirconacyclopentadienes, which have two Zr-C(sp2)
bonds in one molecule, with PhPCl2 afforded cyclic
phosphorus compounds.3 In contrast, acyclic R-substi-
tuted alkenylzirconocene compounds such as 1 do not
react with Ph2PCl to afford alkenylphosphines.4 In this
paper, we report that reactions of alkenylzirconocene 1
with R′2PCl were realized in the presence of CuCl.
Unexpectedly, in this reaction the Cu(I) complex 2 with
the tethered olefin-phosphine compound 3 as a biden-
tate ligand was obtained.
* To whom correspondence should be addressed. E-mail: tamotsu@
cat.hokudai.ac.jp.
† Hokkaido University.
‡ Peking University.
§ Aichi University of Education.
(1) (a) Takahashi, T.; Kotora, M.; Hara, R.; Xi, Z. Bull. Chem. Soc.
J pn. 1999, 72, 2591. (b) Kotora, M.; Xi, Z.; Takahashi, T. J . Synth.
Org. Chem. J pn. 1997, 55, 958.
Resu lts a n d Discu ssion
Transmetalation of Zr-C(sp2) bonds to Cu-C(sp2)
bonds using CuCl has proven very efficient for novel
organic transformation reactions.1 The trisubstituted
alkenylzirconocenes 15 did not react with Ph2PCl, even
at high temperature. When CuCl was added, the reac-
tion proceeded rapidly and cleanly (Scheme 1). Trans-
metalation of Zr-C(sp2) bonds to Cu-C(sp2) bonds is
essential for this reaction. Very interestingly, the in situ
(2) (a) Nishihara, Y.; Aoyagi, K.; Hara, R.; Suzuki, N.; Takahashi,
T. Inorg. Chim. Acta 1996, 252, 91. (b) Aoyagi, K.; Kasai, K.; Kondakov,
D. Y.; Hara, R.; Suzuki, N.; Takahashi, T. Inorg. Chim. Acta 1994,
220, 319. See also: (c) Mirza-Aghayan, M.; Boukherroub, R.; Etemad-
Moghadam, G.; Manuel, G.; Koenig, M. Tetrahedron Lett. 1996, 37,
3109. (d) Mirza-Aghayan, M.; Boukherroub, R.; Oba, G.; Manuel, G.;
Koenig, M. J . Organomet. Chem. 1998, 564, 61.
(3) (a) Fagan, P. J .; Nugent, W. A. J . Am. Chem. Soc. 1988, 110,
2130. (b) Fagan, P. J .; Nugent, W. A.; Calabrese, J . C. J . Am. Chem.
Soc. 1994, 116, 1880. (c) Zablocka, M.; Cenac, N.; Igau, A.; Donnadieu,
B.; Majoral, J . P.; Skowronska, A.; Meunier, P. Organometallics 1996,
15, 5436.
(5) (a) Kasai, K.; Kotora, M.; Suzuki, N.; Takahashi, T. J . Chem.
Soc., Chem. Commun. 1995, 109. (b) Takahashi, T.; Kotora, M.; Kasai,
K. Tetrahedron Lett. 1994, 35, 5685.
(4) (a) Taapken, T.; Blechert, S. Tetrahedron Lett. 1995, 36, 6659.
(b) Zhong, P.; Huang, X.; Xiong, Z. Synlett 1999, 6, 721.
10.1021/om000592u CCC: $20.00 © 2001 American Chemical Society
Publication on Web 06/01/2001

2860 Organometallics, Vol. 20, No. 13, 2001
Miyaji et al.
F igu r e 1. ORTEP drawing of 2a . The symmetry-equivalent atoms, which are labeled with asterisks, are generated by
the symmetry operator 1 - x, -y, 2 - z.
F igu r e 2. ORTEP drawing of complex 2c. The symmetry-equivalent atoms, which are labeled with asterisks, are generated
by the symmetry operator 2 - x, -y, 2 - z.
formed tethered olefin-phosphine compounds behaved
as chelating ligands and coordinated with the regener-
ated CuCl to afford Cu(I) complexes, providing a direct
synthesis of Cu(I) complexes.6-8 Copper(I) complexes 2a
(R ) n-Pr, R′ ) Ph), 2b (R ) n-Pr, R′ ) i-Pr), and 2c (R
) Ph, R′ ) i-Pr), were formed in 83%, 72%, and 85%
yields, respectively. Purification by column gave pure
compounds in 43%, 50%, and 55% yields, respectively.
Copper(I) complexes with olefin ligands are of great
importance in biochemistry and synthetic organic chem-
istry.9,10 The simultaneous coordination of the olefin
moiety and the phosphorus atom in a tethered phos-
phine-olefin to a metal center is rare.6-8 There is only
one structurally characterized Cu(I) complex of this
kind,8d to our knowledge. In the literature case, CuBr2
was used as the copper source and reduced in methanol
upon coordination.8d
The X-ray single-crystal structures of 2a and 2c are
given in Figures 1 and 2, respectively, which show that
these complexes are chlorine-bridged dimers with the
copper atom bonded to two chloride ions, the tertiary
phosphine, and the double bond of the olefin. The C-C
distances of the terminal double bond in 2a and 2c are
(6) We have recently reported a zirconocene complex with a tethered
olefin-phosphine ligand: Yamazaki, A.; Nishihara, Y.; Nakajima, K.;
Hara, R.; Takahashi, T. Organometallics 1999, 18, 3105.
(7) For transition-metal complexes with tethered P-olefins or N-
olefins for Ru, Rh, Ir, Pd, Pt, and W, see the references cited in ref 6.
(8) For Cu(I) complexes with tethered P-olefins or N-olefins: (a)
Yingst, R. E.; Pouglas, B. E. Inorg. Chem. 1964, 3, 1177. (b) Bennett,
M. A.; Kneen, W. R.; Nyholm, R. S. Inorg. Chem. 1968, 7, 552. (c)
Fukushima, K.; Kobayashi, A.; Miyamoto, T.; Sasaki, Y. Bull. Chem.
Soc. J pn. 1976, 49, 143. (d) Alyea, E. C.; Meehan, P. R.; Ferguson, G.;
Kannan, S. Polyhedron 1997, 16, 3479. (e) Zhang, J .; Xiang, R.-G.; You,
X.-Z. Chem. Commun. 2000, 16, 1495. See also: (f) Straub, B. F.;
Eisentrager, F.; Hofmann, P. Chem. Commun. 1999, 2507.
(9) (a) Mori, S.; Nakamura, E. Chem. Eur. J . 1999, 5, 1534. (b) Diaz-
Requejo, M. M.; Belderrain, T.; Nicasio, M. C.; Prieto, F.; Perez, P. J .
Organometallics 1999, 18, 2601.
(10) (a) Schaller, G. E.; Bleecker, A. B. Science 1995, 270, 1809. (b)
Rodriguez, F. I.; Esch, J . J .; Hall, A. E.; Binder, B. M.; Schaller, G. E.;
Bleecker, A. B. Science 1999, 283, 996.

Cu(I) Complexes with an Olefin-Phosphine Ligand
Organometallics, Vol. 20, No. 13, 2001 2861
Sch em e 2
Sch em e 3
Exp er im en ta l Section
All reactions involving organometallic compounds were
carried out under nitrogen. Tetrahydrofuran (THF) was
distilled and dried with sodium benzophenone ketyl. Zircono-
cene dichloride was purchased from Nichia Corp. EtMgBr (0.96
M solution in THF), EtMgCl (0.97 M solution in THF), t-BuLi
(1.50 M soluton in hexane), and chlorodiphenylphosphine were
purchased from Kanto Chemical Co. Inc. Other phosphine
compounds were purchased from Aldrich Chemical Co., Inc.
Alkynes and olefins were purchased from TCI Co. Ltd. Unless
otherwise noted, chemicals were used without further purifica-
tion.
1.360(9) and 1.353(4) Å, respectively, which do not differ
significantly from the corresponding data reported
(1.362(6) Å in a Cu(I)-ethylene complex,8f 1.34(2) Å in
a Cu(I) complex with N-olefin ligands8c) but are shorter
than that in an analogous zirconocene complex (1.435(3)
Å)6 and longer than that in the aforementioned litera-
ture case (1.262(9) Å).8d The distances of 2.307(1) Å
(Cu(1)-Cl(1)), 2.241(1) Å (Cu(1)-P(1)), 2.180(5) Å (Cu(1)-
C(1)), and 2.222(6) Å (Cu(1)-C(2)) for 2a and 2.3926(8)
Å (Cu(1)-Cl(1)), 2.2486(7) Å (Cu(1)-P(1)), 2.203(3) Å
(Cu(1)-C(4)), and 2.216(3) Å (Cu(1)-C(5)) for 2c all lie
within reasonable range.
1H and 13C NMR spectra were recorded on a 400 MHz
Bruker NMR spectrometer.
{[(5-(E)-P r op yl-4,7-octa d ien -4-yl)d ip h en ylp h osp h in e]-
Cu (µ-Cl)}2 (2a ). A 50 mL Schlenk tube was charged with
Cp2ZrCl2 (731 mg, 2.5 mmol) and THF (8 mL) under N2. To
this solution was added EtMgCl (0.97 M, 5.10 mL, 5.0 mmol)
at -78 °C followed by stirring for 1 h. After addition of 4-octyne
(296 µL, 2.0 mmol), the mixture was gradually warmed to 0
°C and stirred for 3 h. To the orange reaction mixture was
added (allyloxy)trimethylsilane (0.69 mL, 4.0 mmol) at 0 °C,
and then the mixture was warmed to 50 °C and stirred for 3
h. To the mixture cooled to 0 °C were added CuCl (223 mg,
2.25 mmol) and Ph2PCl (376 µL, 2.0 mmol). After it was stirred
for 2 h at room temperature, the light orange reaction mixture
was quenched with 3 N HCl and the pale yellow aqueous layer
was extracted with ethyl acetate. The extract combined with
the organic layer was washed with brine and dried over
MgSO4. The title compound was obtained from column chro-
matography (1/3 ethyl acetate/hexane) as a white solid (387
mg, 0.43 mmol, 43% isolated yield). Mp: 150-152° dec. NMR
yield: 83%. 1H NMR (CDCl3, Me4Si): δ 0.46 (t, J ) 7.2 Hz,
6H), 0.61-0.77 (m, 4H), 1.01 (t, J ) 7.3 Hz, 6H), 1.46-1.63
(m, 4H), 2.02-2.31 (m, 8H), 3.01 (d, J ) 5.5 Hz, 4H), 4.40-
4.58 (m, 4H), 5.02-5.22 (m, 2H), 7.17-7.62 (m, 20H). 13C NMR
(CDCl3, Me4Si): δ 14.09, 14.38, 21.62, 23.31, 33.78, 38.55 (d),
38.84 (d), 89.78 (d), 111.77, 125.04 (d), 128.60 (d), 129.93,
131.19 (d), 133.63 (d), 155.09 (d). 31P NMR (CDCl3, H3PO4): δ
-5.07. IR (Nujol, cm-1): 1599 (m), 1558 (m), 1375 (m), 1095
(s), 898 (m), 744 (s), 698 (s). Anal. Calcd for C46H58Cl2Cu2P2:
C, 63.44; H, 6.71; Cl, 8.14. Found: C, 63.52; H, 6.81; Cl, 8.02.
{[(5-(E )-P r op yl-4,7-oct a d ie n -4-yl)d iisop r op ylp h os-
p h in e]Cu (µ-Cl)}2 (2b). The reaction was carried out in the
same way as described above using iPr2PCl (1.0 M, THF
solution, 2.0 mL, 2.0 mmol) instead of Ph2PCl. The desired
complex 2b was formed in 72% NMR yield. Isolation and
purification by column chromatography on silica gel (1/12 ethyl
acetate/hexane) afforded 2b as a colorless solid (366 mg, 0.50
mmol, 50% isolated yield). Mp: 65-67 °C. 1H NMR (CDCl3,
Me4Si): δ 0.90-1.02 (m, 12H), 1.10 (dd, J ) 7.0, 15.5 Hz, 12H),
1.34 (dd, J ) 6.9, 16.9 Hz, 12H), 1.48-1.52 (m, 8H), 2.11-
2.28 (m, 12H), 2.96 (d, J ) 6.1 Hz, 4H), 4.28-4.38 (m, 4H),
4.90-5.02 (m, 2H). 13C NMR (CDCl3, Me4Si): δ 13.89, 14.41,
19.45 (d), 19.88 (d), 20.86, 23.70 (d), 23.91, 33.04, 37.61 (d),
38.72 (d), 86.27, 109.45, 125.39 (d), 156.75 (d). 31P NMR
(CDCl3, H3PO4): δ 15.3. IR (Nujol, cm-1): 1593 (m), 1545 (m),
1381 (s), 1101 (s), 873 (s), 675 (m). Anal. Calcd for C34H66Cl2-
Cu2P2: C, 55.57; H, 9.05; Cl, 9.65. Found: C, 55.61; H, 9.03;
Cl, 9.65.
As a control experiment, free tethered phosphine-
olefin compound 3a (R ) n-Pr, R′ ) Ph) was prepared
in an alternative way from alkenylzirconocenes 1a
(Scheme 2). Addition of 1 equiv of CuCl to a THF
solution of 3a afforded 2a in quantitative NMR yield.
Interestingly, phosphine-olefin compounds 5 and 7
behaved only as monodentate ligands toward CuCl,
forming complexes 6 and 8 in 75% and 73% isolated
yields, respectively. A plausible explanation of this
result is that ligands 3 possess a favorable conformation
for chelating the Cu(I) atom due to the double bond in
the chain between the phosphorus and the olefin moiety.
Comparison of NMR spectral data between the free
ligand 3a and its Cu(I) complex reveals clean formation
1
of the Cu(I) complex 2a . The H NMR spectrum of 2a
shows the chemical shifts of the alkenyl protons are
shifted by 0.5 ppm to higher field.8c,d The 13C NMR
signal of the terminal alkenyl carbon appeared at 89.8
ppm (dCH2) with an upfield shift of 16 ppm compared
with the free ligand 3a .8c,d The 31P NMR spectrum of
2a showed a broad singlet at -5.1 ppm.8d The 31P NMR
chemical shift shows a shift of 5 ppm compared with
the free ligand 3a . These changes in chemical shifts
were all consistent with those reported and indicated
that phosphorus and the terminal double bond coordi-
nate to the Cu atom simultaneously.8c,d,f
When copper-phosphine complex 2a was treated with
2.2 equiv of sodium diethyldithiocarbamate, free phos-
phine 3a was formed in 95% NMR yield and purification
by short-column chlomatography afforded pure 3a in
84% isolated yield (Scheme 3).
{[(1,2-Dip h en yl-1,4-p en t a d ien -1-yl)d iisop r op ylp h os-
p h in e]Cu (µ-Cl)}2 (2c). The reaction was carried out in the

2862 Organometallics, Vol. 20, No. 13, 2001
Miyaji et al.
Ta ble 1. Cr ysta llogr a p h ic Da ta for Com p lexes 2a
a n d 2c
same way as described above, using diphenylacetylene (357
µL, 2.00 mmol) instead of 4-octyne. The desired complex 2c
was formed in 85% NMR yield. Isolation and purification by
column chromatography on silica gel (1/12 ethyl acetate/
hexane) afforded 2c as a colorless solid. Recrystallization from
a THF/hexane mixuture afforded the title compound as color-
less crystals (475 mg, 0.545 mmol, 55% isolated yield). Mp:
2a
2c
formula
Mr
C
46H58Cl2Cu2P2
C46H58Cl2Cu2P2
870.91
870.91
cryst syst
space group
a (Å)
b (Å)
c (Å)
monoclinic
P21/c
monoclinic
P21/n
1
139-141°C dec. H NMR (CDCl3, Me4Si): δ 1.09 (dd, J ) 7.0,
14.8691(9)
10.3391(6)
15.7226(10)
114.650(2)
2
19.8191(2)
8.3541(2)
14.5945(4)
111.162(1)
2
15.9 Hz, 12H), 1.23 (dd, J ) 6.9, 16.7 Hz, 12H), 2.02-2.21 (m,
4H), 3.45 (d, J ) 6.1 Hz, 4H), 4.46-4.58 (m, 4H), 5.25-5.40
(m, 2H), 6.63-7.07 (m, 20H). 13C NMR (CDCl3, Me4Si): δ 19.07
(d), 19.63 (d), 23.99 (d), 40.93 (d), 90.16 (d), 110.65, 126.45,
126.51, 127.65, 127.70, 127.73, 129.70, 131.28 (d), 139.32 (d),
144.18 (d), 158.35 (d). 31P NMR (CDCl3, H3PO4): δ 9.75. IR
(Nujol, cm-1): 1599 (m), 1560 (m), 1379 (m), 1263 (m), 1024
(s), 883 (s), 802 (s), 765 (s), 700 (s). Anal. Calcd for C48H58Cl2-
Cu2P2 C, 63.44; H, 6.71; Cl, 8.14. Found: C, 63.38; H, 6.78;
Cl, 8.21.
â (deg)
Z
V (Å3)
2196.8(2)
11.94
2253.47(9)
11.63
µ(Mo KR) (cm-1
)
cryst size (mm3)
0.20 × 0.30 × 0.40 0.30 × 0.30 × 0.50
Dcalcd (g cm-3
F(000)
)
1.32
912
1.283
912
no. of rflns measd
no. of unique rflns (Rint
12 963
5032 (0.026)
13 114
9970 (0.028)
7014
351
0.053
0.068
)
no. of rflns obsd (I > 2σ(I)) 3259
(5-(E)-P r opyl-4,7-octadien -4-yl)diph en ylph osph in e (3a).
To the copper-phosphine complex 2a (89.7 mg, 0.0996 mmol)
were added sodium diethyldithiocarbamate trihydrate (49.7
mg, 0.221 mmol) and 5 mL of THF. The solution changed from
colorless to dark yellow immediately. After the mixture was
stirred for 2 h at room temperature, the solvent was removed
in vacuo. The desired compound 3a was formed in 95% NMR
yield. The purification through silica gel short-column chro-
matography (1/25 ethyl acetate/hexane) gave free phosphine
3a in 84% isolated yield (58.8 mg, 0.167 mmol). 1H NMR
(CDCl3, Me4Si): δ 0.45 (t, J ) 7.4 Hz, 3H), 0.62-0.73 (m, 2H),
0.97 (t, J ) 7.3 Hz, 3H), 1.47-1.61 (m, 2H), 2.05-2.16 (m, 2H),
2.17-2.27 (m, 2H), 3.39-3.46 (m, 2H), 4.96-5.10 (m, 2H),
5.72-5.86 (m, 1H), 7.18-7.52 (m, 10H). 13C NMR (CDCl3,
Me4Si): δ 14.17, 14.39, 21.81, 23.36, 33.77 (d), 34.71 (d), 38.36
(d), 115.54, 127.70 (d), 128.00, 130.37 (d), 133.06 (d), 136.63,
137.67 (d), 152.16 (d). 31P NMR (CDCl3, H3PO4): δ -9.95. IR
(Nujol, cm-1): 1635 (m), 1597 (m), 1182 (m), 1114 (m), 1089
(m), 1068 (m), 1026 (m), 995 (m), 912 (s), 742 (s), 696 (s).
Dip h en yl(4-p en ten -1-yl)p h osp h in e (5). 1H NMR (CDCl3,
Me4Si): δ 1.46-1.62 (m, 2H), 1.98-2.23 (m, 4H), 4.89-5.06
(m, 2H), 5.68-5.82 (m, 1H), 7.20-7.68 (m, 10H). 13C NMR
(CDCl3, Me4Si): δ 25.15 (d), 27.35 (d), 35.02 (d), 115.05, 128.33
(d), 128.33, 132.61 (d), 138.00, 138.77 (d). 31P NMR (CDCl3,
Ph3P): δ -16.86. IR (Nujol, cm-1): 1639 (m), 1186 (m), 1118
(m), 1097 (m), 1068 (m), 1026 (m), 999 (m), 912 (s), 738 (s),
696 (s).
no. of params refined
235
0.054
0.069
Ra
Rw
b
a
b
2
R ) ∑||Fo| - |Fc||/∑|Fo|. Rw ) [∑w(|Fo| - |Fc|)2/∑w|Fo| ]1/2, w
2
2
) [σc (Fo) + (p2/4)|Fo| ]-1
.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 2a
Cu(1)-P(1)
Cu(1)-C(2)
Cu(1)-Cl(1)
2.241(1)
2.222(6)
2.307(1)
Cu(1)-C(1)
C(1)-C(2)
Cu(1)-Cl(1*)
2.180(5)
1.360(9)
2.557(1)
C(1)-Cu(1)-C(2)
P(1)-Cu(1)-Cl(1)
36.0(2) C(1)-C(2)-C(3)
129.1(8)
113.56(5)
117.82(4) P(1)-Cu(1)-Cl(1*)
Cl(1)-Cu(1)-Cl(1*) 96.83(4) Cu(1)-Cl(1)-Cu(1*) 83.17(4)
P(1)-Cu(1)-C(1)
121.2(2) P(1)-Cu(1)-C(2)
92.4(2)
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 2c
Cu(1)-P(1)
Cu(1)-C(4)
Cu(1)-Cl(1)
2.2486(7)
2.203(3)
2.3926(8)
Cu(1)-C(5)
C(4)-C(5)
Cu(1)-Cl(1*)
2.216(3)
1.353(4)
2.40107(8)
C(4)-Cu(1)-C(5)
P(1)-Cu(1)-Cl(1)
35.7(1) C(3)-C(4)-C(5)
126.5(4)
111.18(3)
117.12(3) P(1)-Cu(1)-Cl(1*)
Cl(1)-Cu(1)-Cl(1*) 96.50(2) Cu(1)-Cl(1)-Cu(1*) 83.50(2)
P(1)-Cu(1)-C(5)
126.35(9) P(1)-Cu(1)-C(4)
90.74(8)
[Dip h en yl(4-p en ten -1-yl)p h osp h in e]Cu Cl (6). To a sus-
pension of CuCl (50.1 mg, 0.51 mmol) in THF (5 mL) was
added diphenyl(4-penten-1-yl)phosphine (129 mg, 0.51 mmol),
and then the mixture was stirred at room temperature for 6
h. After the solvent was removed in vacuo, the residue was
extracted with chloroform through flash column chromatograpy
on silica gel. Removal of the solvent in vacuo gave the title
compound as a colorless oil (134 mg, 75% isolated yield). NMR
yield: 92%. 1H NMR (CDCl3, Me4Si): δ 1.62-1.83 (m, 2H),
1.97-2.29 (m, 4H), 4.74-4.92 (m, 2H), 5.46-5.63 (m, 2H),
7.16-7.38 (m, 6H), 7.60-7.79 (m, 4H). 13C NMR (CDCl3,
Me4Si): δ 24.00 (d), 26.51 (d), 34.74 (d), 111.65, 128.39 (d),
129.58, 132.87 (d), 133.34 (d), 134.23. 31P NMR (CDCl3,
Ph3P): δ -11.41. IR (Nujol, cm-1): 1639 (m), 1242 (s), 1186
(w), 1101 (s), 1045 (m), 1028 (m), 999 (m), 914 (s), 740 (s), 696
(s).
(3-P r opyl-(3E)-pen ten yl)diph en ylph osph in e (7). 1H NMR
(CDCl3, Me4Si): δ 0.83-0.93 (m, 6H), 1.24-1.38 (m, 4H), 1.90-
2.16 (m, 8H), 5.15 (t, J ) 7.1 Hz, 1H), 7.27-7.35 (m, 6H), 7.38-
7.46 (m, 4H). 13C NMR (CDCl3, Me4Si): δ 13.89, 14.10, 21.48,
23.12, 26.98 (d), 29.78, 31.97, 32.89 (d), 125.25, 128.34 (d),
128.34, 132.69 (d), 138.81 (d), 139.35 (d). 31P NMR (CDCl3,
H3PO4): δ -15.97. IR (Nujol, cm-1): 1589 (m), 1186 (m), 1143
(m), 1099 (s), 1070 (m), 1028 (m), 999 (m), 941 (m), 893 (m),
738 (s), 694 (s). HRMS: m/z calcd for C22H29P 324.2007, found
324.2027.
{[(3-P r opyl-(3E)-pen ten yl)]diph en ylph osph in e}Cu Cl (8).
The reaction was carried out in the same way as described in
the case of 6, using 7 instead of 5. NMR yield: 89%. Isolated
yield: 73%. 1H NMR (CDCl3, Me4Si): δ 0.74 (t, J ) 7.4 Hz,
3H), 0.84 (t, J ) 7.4 Hz, 3H), 1.16-1.32 (m, 4H), 1.83-1.96
(m, 4H), 2.17-2.32 (m, 4H), 5.10 (t, J ) 7.1 Hz, 1H), 7.18-
7.32 (m, 6H), 7.59-7.73 (m, 4H). 13C NMR (CDCl3, Me4Si): δ
13.81, 13.97, 21.35, 22.95, 26.64 (d), 29.71, 31.80, 31.85, 125.15,
128.29 (d), 129.38, 132.88 (d), 133.59 (d), 139.09 (d). 31P NMR
(CDCl3, H3PO4): δ -10.92. IR (Nujol, cm-1): 1587 (m), 1377
(m), 1186 (m), 1143 (m), 1099 (s), 1070 (m), 1028 (m), 999 (m),
941 (m), 910 (m), 893 (m), 736 (s), 694 (s).
X-r a y Cr ysta llogr a p h y. A colorless prismatic crystal of 2a
or 2c having approximate dimensions of 0.2 × 0.3 × 0.4 mm3
for 2a and 0.30 × 0.30 × 0.50 mm3 for 2c was mounted in a
glass capillary and sealed under argon. X-ray data were
collected on a Rigaku RAXIS-RAPID diffractometer with
graphite-monochromated Mo KR radiation (λ ) 0.710 69 Å).
A total of 44 images were collected with 2 different goniometer
settings. Data were processed by the PROCESS-AUTO pro-
gram package. The linear absorption coefficients, µ, for Mo KR
radiation were 11.94 cm-1 for 2a and 11.63 cm-1 for 2c, and a
numerical absorption correction using the program NUMABS11
(11) Higashi, T. Program for Absorption Correction; Rigaku Corp.,
Tokyo, J apan, 1999.

Cu(I) Complexes with an Olefin-Phosphine Ligand
Organometallics, Vol. 20, No. 13, 2001 2863
was applied. The structures were solved by direct methods
(SIR9212) and expanded using Fourier techniques (DIRDIF9413).
The non-hydrogen atoms were refined anisotropically. The
hydrogen atoms of 2c were located from difference maps and
refined isotropically, while those of complex 2a were placed
in calculated positions. All calculations were performed using
the teXsan14 crystallographic software package of Molecular
Structure Corp.
Ack n ow led gm en t. Part of this work was supported
by the Ministry of Education, Science, Sport and Culture
of J apan. Z.X. thanks the National Natural Science
Foundation of China (Grant No. 29702001), the Na-
tional Science Fund for Distinguished Young Scholars
(Grant No. 29825105), and the Peking University
President Fund for financial support for part of this
work.
Table 1 gives crystallographic data for complexes 2a and
2c, while Tables 2 and 3 give bond distances and angles for
2a and 2c, respectively.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal-
lographic data and data collection and solution and refinement
details, positional and thermal parameters, and bond distances
and angles for 2a and 2c. This material is available free of
charge via the Internet at http://pubs.acs.org.
(12) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, M.;
Giacovazzo, C.; Guagliardi, A.; Polidori, G. J . Appl. Crystallogr. 1994,
27, 435.
(13) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
de Gelder, R.; Israel, R.; Smits, J . M. M. The DIRDIF-94 Program
System; Technical Report of the Crystallography Laboratory; Univer-
sity of Nijmegen, Nijmegen, The Netherlands, 1994.
(14) Crystal Structure Analysis Package; Molecular Structure Corp.,
The Woodlands, TX, 1985 & 1999.
OM000592U