2128 Organometallics, Vol. 19, No. 11, 2000
Yagyu et al.
Ta ble 1. Cr ysta llogr a p h ic Da ta a n d Deta ils of
The reaction probably involves an intermediate Pd
complex containing the cyclic acetylene as the tertiary
alkyl ligand similarly to 2.
Refin em en t of 2‚a ceton e
chemical
formula
fw
C39H41BF4N2O13Pd µ, cm-1
5.237
960
1.482
F(000)
In summary, the cationic and neutral arylpalladium
complexes with a bipyridine ligand react with DMAD
at different rates to give 2 and 3, repsectively. The
neutral arylpalladium complex 1 with an iodo ligand
reacts with DMAD, whereas the vinylpalladium complex
3 does not cause further insertion of the carbon-carbon
triple bond. Upon treatment with AgBF4, complexes 1
and 3 react readily with DMAD to undergo the insertion
of three or two acetylene molecules into the Pd-C bond.
938.96
D
calcd, g cm-3
cryst syst
space group P1h (No. 2)
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
triclinic
cryst size, mm
0.75 × 0.28
× 0.15
5.0-55.0
9677
14.113(4)
15.078(4)
10.365(3)
100.76(2)
101.28(2)
96.56(2)
2105(1)
2
2θ range, deg
no. of unique
reflns
no. of reflns used 5271
(I g 3σ(I))
no. of variables
508
0.064
0.061
R(Fo)a
Rw(Fo)a
a
Weighting scheme, [{σ(Fo)}2]-1
.
Exp er im en ta l Section
Gen er a l Con sid er a tion , Mea su r em en t, a n d Ma ter ia ls.
Manipulations of the palladium complexes were carried out
under nitrogen or argon using standard Schlenk techniques.
(85%). Anal. Calcd for BC36F4H35N2O12Pd‚CH2Cl2: C, 46.01;
H, 3.86; N, 2.90. Found: C, 46.22; H, 4.09; N, 2.86.
P r ep a r a tion of 3. A mixture of [PdI(C6H3Me2-3,5)(bpy)] (55
mg, 0.11 mmol) and DMAD (72 mg, 0.51 mmol) in 10 mL of
dry acetone was stirred for 24 h at room temperature. After
the removal of a small amount of insoluble solid by filtration,
the solvent was removed under reduced pressure. Recrystal-
lization of the remaining solid from CH2Cl2-hexane yielded 3
as yellow crystals (53 mg, 75%). Anal. Calcd for C24H23IN2O4-
Pd: C, 45.27; H, 3.64; N, 4.40; I, 19.93. Found: C, 45.50; H,
1
NMR spectra (1H, 13C{1H}, 1H-1H COSY, and H-13C COSY)
were recorded on J EOL EX-400 and Lambda-500 spectrom-
eters. Elemental analyses were carried out with a Yanaco
MT-5 CHN autocorder. Complex 1 was prepared according to
the literature method to prepare analogous arylpalladium
complexes as follows.12 To a benzene solution (15 mL) of Pd-
(dba)2 (2.25 g, 3.91 mmol) were added bpy (826 mg, 5.29 mmol)
and 3,5-Me2C6H3I (0.90 mL, 0.62 mmol). The mixture was
stirred for 3 h with gentle heating below 50 °C. After
evaporation of the solvent, the CH2Cl2-soluble fraction of the
product was recrystallized from CH2Cl2-hexane to give 1 (1.03
g, 53.2%). Anal. Calcd for C18H17IN2Pd: C, 43.71; H, 3.46; N,
1
3.76; N, 4.37; I, 19.55. H NMR (500 MHz, CDCl3): δ 2.07 (s,
6H, CH3C6H3), 3.68 (s, 3H, OCH3), 3.81 (s, 3H, OCH3), 6.65 (s,
1H, p-C6H2H), 7.24 (m, 1H, H5-bpy), 7.30 (s, 2H, o-C6HH2), 7.43
(m, 1H, H5′-bpy), 7.80 (d, 1H, H3′-bpy, J ) 8.2 Hz), 7.87 (m,
1H, H4′-bpy), 7.88 (d, 1H, H3-bpy, J ) 8 Hz), 7.91 (m, 1H, H4-
bpy), 8.80 (d, 1H, H6′-bpy, J ) 5.5 Hz), 9.35 (d, 1H, H6-bpy, J
) 4.6 Hz). 13C{1H} NMR (125 MHz, CDCl3): δ 21.2 (CH3C6H3),
51.8 (OCH3), 52.0 (OCH3), 122.2 (C3′-bpy), 122.2 (C3-bpy), 126.2
(C5′-bpy), 126.5 (C5-bpy), 128.0 (o-C6H3), 128.6 (p-C6H3), 134.5,
136.5, 138.9 (C4′-bpy), 139.3, 139.4 (C4-bpy), 151.0 (C6′-bpy),
153.2 (C6-bpy), 153.6, 155.2, 158.2, 164.3, 173.3.
1
5.66; I, 25.65. Found: C, 43.47; H, 3.50; N, 5.64; I, 25.96. H
NMR (400 MHz, CDCl3): δ 2.19 (s, 6H, CH3C6H3), 6.52 (s, 1H,
p-C6H2H), 6.99 (s, 2H, o-C6HH2), 7.32 (m, 1H, H5′-bpy), 7.47
(m, 1H, H5-bpy), 7.65 (d, 1H, H6′-bpy, J ) 5.9 Hz), 7.96 (m,
2H, H4 and H4′-bpy), 8.06 (m, 2H, H3 and H3′-bpy), 9.56 (d,
1H, H6-bpy, J ) 3.9 Hz).
P r ep a r a tion of 2‚Aceton e. To a dry acetone solution (25
mL) of [PdI(C6H3Me2-3,5)(bpy)] (125 mg, 0.253 mmol) and
DMAD (0.124 mL, 1.01 mmol) was added AgBF4 (71.2 mg,
0.366 mmol). The mixture was stirred at room temperature
to complete the separation of AgI, which was removed by
filtration. The addition of Et2O to the filtrate gave 2 in an
acetone-solvated form (2‚acetone) as yellow crystals (202 mg,
85%). Anal. Calcd for BC36F4H35N2O12Pd‚C3H6O: C, 49.89; H,
4.40; N, 2.98. Found: C, 49.97; H, 4.49; N, 2.79. 1H NMR (500
MHz, CDCl3): δ 1.98 (s(br), 3H, CH3C6H3), 2.12 (s, 6H,
acetone), 2.22 (s(br), 3H, CH3C6H3), 3.66 (s, 3H, OCH3), 3.68
(s, 3H, OCH3), 3.70 (s, 3H, OCH3), 3.77 (s, 3H, OCH3), 3.89 (s,
3H, OCH3), 4.15 (s, 3H, OCH3), 6.85 (s, 1H, p-C6H2H), 7.06
(s(br), 1H, o-C6HH2), 7.10 (m, 1H, H5′-bpy), 7.18 (s(br), 1H,
o-C6HH2), 7.63 (d, 1H, H6′-bpy, J ) 5.8 Hz), 7.77 (m, 1H, H5-
bpy), 8.09 (m, 1H, H4′-bpy), 8.24 (m, 1H, H4-bpy), 8.45 (d, 1H,
H3′-bpy, J ) 8.2 Hz), 8.54 (d, 1H, H3-bpy, J ) 8.2 Hz), 8.60 (d,
1H, H6-bpy, J ) 4.9 Hz). 13C{1H} NMR (125 MHz, CDCl3): δ
21.0 (CH3C6H3), 21.3 (CH3C6H3), 30.8 (CH3-acetone), 49.9, 52.2
(OCH3), 52.5 (OCH3), 52.9 (OCH3), 53.0 (OCH3), 53.1 (OCH3),
57.7 (OCH3), 78.3, 123.9 (C3-bpy), 123.9 (C3′-bpy), 126.3 (C5′-
bpy), 127.8 (C5-bpy), 129.0 (o-C6H3), 129.7 (o-C6H3), 130.1 (p-
C6H3), 132.1, 133.7, 135.4, 136.9, 141.4 (C4′-bpy), 141.6 (C4-
bpy), 146.4, 148.8 (C6-bpy), 150.0, 152.1 (C6′-bpy), 153.3, 157.3,
159.9, 162.2, 163.3, 164.2, 173.7, 185.6, 207.0 (CO-acetone).
Similar reaction in THF and ensuing recrystallization of the
product from CH2Cl2-Et2O gives 2‚CH2Cl2. Yield: 198 mg
Rea ction of 3 w ith DMAD in Aceton e-d 6 in th e P r es-
en ce of AgBF 4. A mixture of 3 (12 mg, 0.019 mmol) and AgBF4
(30 mg, 0.15 mmol) in 0.5 mL of acetone-d6 was stirred for 1
min at room temperature. After the removal of an insoluble
solid by filtration, the solution was transferred to an NMR
1
tube under argon. The H NMR spectrum exhibited signals at
δ 2.08 (s, 6H, CH3C6H3), 3.67 (s, 3H, OCH3), 3.77 (s, 3H, OCH3),
6.76 (s, 1H, p-C6H2H), 7.45 (s, 2H, o-C6HH2), 7.8 (m, 2H, H5
and H5′-bpy), 8.3 (m, 3H, H4, H4′ and H6′-bpy), 8.47 (d, 1H, H3-
bpy, J ) 7.8 Hz), 8.52 (d, 1H, H3′-bpy, J ) 8.3 Hz), 8.69 (d,
1H, H6-bpy, J ) 4.9 Hz), which remained unchanged for 3 days
at room temperature. To this solution was added 6.0 µL (0.049
mmol) of dimethyl acetylenedicarboxylate, after which
a
change of the 1H NMR spectrum was observed for 1 day at
room temperature.
Cr ysta l Str u ctu r e Deter m in a tion . Crystals of 2‚acetone
suitable for X-ray diffraction study were obtained by recrys-
tallization from acetone-Et2O and mounted in glass capillary
tubes under argon. Intensities were collected for Lorentz and
polarization effects on a Rigaku AFC-5R automated four-cycle
diffractometer by using Mo KR radiation (λ ) 0.71069 Å) and
the ω-2θ scan method, and an empirical absorption correction
(Ψ scan) was applied. Calculations were carried out by using
the program package TEXSAN for Windows. Atomic scattering
factors were obtained from the literature.13 Three fluorine
atoms were assigned to the two disordered positions (F2-F7)
with 50:50 occupancy. A full-matrix least-squares refinement
was used for non-hydrogen atoms with anisotoropic thermal
parameters. Hydrogen atoms were located by assuming the
ideal geometry and included in the structure calculation
without further refinement of the parameters. Crystallo-
(12) de Graaf, W.; Smeets, W. J . J .; Spek, A. L.; van Koten, G.
Organometallics 1989, 8, 2907. de Graaf, W.; Boersma, J .; van Koten,
G. Organometallics 1990, 9, 1479. Alsters, P. L.; Engel, P. F.;
Hogerheide, M. P.; Copijn, M.; Spek, A. L.; van Koten, G. Organome-
tallics 1993, 12, 1831. Markies, B. A.; Canty, A. J .; de Graaf, W.;
Boersma, J .; J anssen, M. D.; Hogerheide, M. P.; Smeets, W. J . J .; Spek,
A. L.; van Koten, G. J . Organomet. Chem. 1994, 482, 191.
(13) International Tables for X-ray Crystallography; Kynoch: Bir-
mingham, England, 1974; Vol. 4.