Insertions of Allenes into Pd-C Bonds
Organometallics, Vol. 16, No. 4, 1997 553
Ta ble 1. Cr ysta l Da ta a n d Deta ils of th e Str u ctu r e
Deter m in a tion for
C(O)CH3); 9, 8.22 (s, 2H, Himine), 7.48 (br, 4H, Hortho), 6.86 (d,
3J ) 8.9 Hz, 4H, Hmeta), 3.83, (s, 6H, OCH3), 2.36 (s, 3H, Pd-
C(O)CH3).
13C NMR (75.48 MHz, CDCl3; δ): 8, 58.8 (CHiPr), 34.7
(CH3iPr), 21.2 (C(O)CH3), 225.1 (C(O)CH3), Cimine not observed;
9, 139.5, 125.6, 113.3 (Phanisyl), 54.4 (OCH3), Cimine and acetyl
not observed.
Anal. 8, found (calcd for C10H19ClN2OPd): C, 36.79 (36.94);
H, 5.75 (5.89); N, 8.60 (8.62). 9, found (calcd for C18H19ClN2O3-
Pd): C, 47.44 (47.70); H, 4.18 (4.23); N, 6.14 (6.18).
Gen er a l P r oced u r e for th e Syn th esis of Allyl Com -
p lexes (NkN)P d (η3-a llyl)X (X ) Cl, Br ). To a solution of
(NkN)Pd(R)X (X = Cl, Br) (0.28 mmol) in dichloromethane (20
mL) was added the allene either by a microsyringe or by
bubbling the allene through the solution from a lecture bottle.
After the solution was stirred for about 30 min, the solvent
was removed in vacuo and the product could be isolated in
virtually quantitative yield.
1H NMR data (300 MHz, CDCl3; δ) are as follows. 6b
(numbering scheme presented in Figure 1): acenaphthene,
7.98 (d, 3J ) 8.3 Hz, 2H, H3), 7.48 (t, 3J ) 7.8 Hz, 2H, H2),
7.23 (t, 3J ) 7.8 Hz, 2H, H1); p-anisyl, 7.03 (d, 3J ) 8.8 Hz,
4H, Hmeta), 7.40 (d, 3J ) 8.8 Hz, 4H, Hortho), 3.90 (s, 6H, OCH3);
allyl, 4.82 (t, 3J ) 7.2 Hz, 1H, Hanti), Hsyn and Hanti not observed;
(8-P Q)P d {(1-3-η)-2-m eth ylp r op en yl}Cl (1a )
Crystal Data
empirical formula
fweight
C18H17ClN2Pd
403.22
cryst system
space group
a-c, Å
triclinic
P1h (No. 2)
9.2427(13), 11.211(2), 15.966(8)
88.19(3), 88.76(3), 89.728(12)
1653.2(9)
R-γ, deg
V, Å3
D
Z
calc, g‚cm-3
1.620
4
F(000)
808
12.8 (Mo KR)
µ, cm-1
cryst size, mm
0.08 × 0.20 × 0.30
Data Collection
T, K
150
θ
min, θmax, deg
1.3, 27.5
wavelength, Å
0.710 73 (Mo KR) (graphite monochr)
ω/2θ, 0.84 + 0.35 tan θ
2h21, 2h2h5, 1h3h2
-12 to 12, -14 to 14, -13 to 20
9113, 7582, 0.0382
5495
scan type; scan, deg
ref reflcns
data set
tot., uniq data, R(int)
obsd data [I > 2.0σ(I)]
Refinement
7574, 399
0.0732, 0.1682, 1.14
0.001
3
3
n-butyl, 0.71 (t, J ) 7.1 Hz, 3H, CH3), 1.04 (q, J ) 7.1 Hz,
N
ref, Nparam
2H, CH2), 1.24 (br, 2H, CH2), 1.42 (br, 2H, CH2), 2.16 (s, 3H,
R, wR,a
(∆/σ)max
S
3
C(O)CH3). 7b: acenaphthene, 7.98 (d, J ) 8.0 Hz, 2H, H3),
7.57 (t, 3J ) 8.2 Hz, 2H, H2), 7.17 (t, 3J ) 7.3 Hz, 2H, H1),
min and max F, e Å-3
-1.21, 1.59
6.99 (m, 6H, Hmeta, HC(O)Ph), 7.41 (m, 7H, Hortho, HC(O)Ph), 3.89
a
2
w ) 1/[σ2(Fo2) + (0.0202P)2 + 24.296P], P ) (Fo + 2Fo2)/3.
3
(s, 6H, OCH3); allyl, 4.82 (t, J ) 7.2 Hz, 1H, Hanti), 3.90 (br,
1H, Hsyn), 3.51 (br, 1H, Hanti); n-butyl, 0.68 (t, 3J ) 7.1 Hz,
evaporated under vacuo. The solid was washed twice with
ether yielding 130 mg (0.26 mmol, 95%) of product.
Anal. Found (calcd for C18H15F3N2O3SPd): C, 43.43 (42.99);
H, 3.46 (3.01); N, 5.60 (5.57).
3H, CH3), 0.90 (br, 2H, CH2), 1.06 (br, 2H, CH2), 1.26 (br, 2H,
CH2). 9b: DAB, 8.62 (br, 2H, Himine); p-anisyl, 7.46 (d, J )
8.3 Hz, Hortho), 6.94 (d, J ) 8.3 Hz, Hmeta), 3.84 (s, 6H, OCH3)
3
3
allyl: 5.17 (br, 1H, Hanti), 3.35 (br, 1H, Hsyn), 3.30 (br, 1H, Hanti);
n-butyl, 0.81 (t, 3J ) 7.1 Hz, 3H, CH3), 1.26 (br, 2H, CH2),
1.40 (br, 2H, CH2), 1.60 (br, 2H, CH2), 2.36 (s, 3H, C(O)CH3).
13C-NMR (75.48 MHz, CDCl3; δ) are as follows. 6b: p-An-
BIAN, 163.6, 159.0, 143.2, 131.8, 130.8, 128.6, 128.5, 124.9,
122.0, 115.5, 56.3 (OCH3); allyl, CH, CH2, and Ccentral not
observed, 25.7 (C(O)CH3), 195.1 (C(O)CH3); n-butyl, 32.9, 30.5,
22.8 (CH2), 14.4 (CH3). 7b: p-An-BIAN, 164.2, 158.6, 142.4,
130.8, 130.3, 129.5, 128.7, 122.7, 121.9, 56.0 (OCH3); allyl, CH,
CH2, and Ccentral not observed, 141.0, 128.6, 124.7 (C(O)C6H6),
194.0 (C(O)C6H6); n-butyl, 32.7, 31.1, 22.7 (CH2), 14.3 (CH3).
9b: DAB, 158.2 (Cimine); p-anisyl, 160.1, 142.6, 123.4, 114.4,
55.4 (OCH3); allyl, CH and CH2 not observed, 118.1 (Ccentral),
25.7 (C(O)CH3), 194.8 (C(O)CH3); n-butyl, 31.9, 29.9, 21.9
(CH2), 13.4 (CH3).
Gen er a l P r oced u r e for th e Syn th esis of Allyl Com -
p lexes (NkN)P d (η3-a llyl)X (X ) BF 4, OTf). After insertion
of the allene as decribed above, an excess of NaX (X ) BF4,
OTf) was added to a solution of the complex in dichlo-
romethane (20 mL). After 2 h the suspension was filtered and
the solvent was removed in vacuo providing the product
isolated in yields up to 95%.
1H NMR data (300 MHz, CDCl3; δ) are as follows. 15: i-Pr-
3
DAB, 8.52 (s, 2H, Himine), 4.06 (sept, J ) 6.3 Hz, 2H, CHiPr),
1.35 (t, 3J ) 6.1 Hz, 6H, CH3iPr); allyl, 5.70 (t, 3J ) 7.0 Hz, 1H,
H
syn), 4.65 (s, 1H, Hanti), 3.56 (s, 1H, Hanti), 2.42 (s, 3H, C(O)-
CH3); n-butyl, 1.92 (m, 2H, CH2), 1.57 (m, 2H, CH2), 0.91 (m,
3H, CH3). 16 (numbering scheme presented in Figure 1): i-Pr-
PyCa, 9.00 (s, 1H, Himine), 8.97 (d, 3J ) 5.7, 1H, H2), 7.82 (t, 3J
3
) 5.7 Hz, 1H, H3), 8.16 (t, 7.8, 1H, H4), 8.25 (d, J ) 7.7, 1H,
Anal. 1a , found (calcd for C18H17ClN2Pd): C, 53.63 (53.62);
H, 4.29 (4.25); N, 6.98 (6.95). 1b, found (calcd for C22H25ClN2-
Pd): C, 57.36 (57.53); H, 5.42 (5.49); N, 6.01 (6.10). 2a , found
(calcd for C18H17BrN2Pd): C, 48.76 (48.29); H, 3.88 (3.83); N,
6.10 (6.25). 6b, found (calcd for C35H35ClN2O3Pd‚CH2Cl2): C,
57.63 (57.01); H, 5.01 (4.92); N, 4.24 (3.69).
H5), 1.36, 1.32 (d, 3J ) 6.1 Hz, 6H, CH3iPr), 4.16 (sept, 3J )
6.1, 1H, CHiPr); allyl, 5.75 (br, 1H, Hsyn), 4.72 (br, 1H, Hanti),
3.46 (br, 1H, Hanti), 2.46 (s, 3H, C(O)CH3); n-butyl, 1.90 (m,
3
2H, CH2), 1.60 (m, 2H, CH2), 0.88 (t, J ) 7.3 Hz, 3H, CH3).
13C NMR data (75.48 MHz, CDCl3; δ) are as follows. 15:
i-Pr-DAB: 165.1 (Cimine), 63.6 (CHiPr), 23.1 (CH3iPr); allyl, 55.0
(CH2), 116.6 (Ccentral), 85.3 (CH), 26.3 (C(O)CH3), 193.9 (C(O)-
CH3); n-butyl:,32.9, 30.8, 22.3 (CH2), 13.9 (CH3). 16: i-Pr-
PyCa, 166.0 (Cimine), 152.5, 140.3, 128.9, 128.2 (Cpyridyl), 61.9
(CHiPr), 22.3 (CH3iPr); allyl, CH2, CH and Ccentral not observed,
22.3 (C(O)CH3), 193.7 (C(O)CH3); n-butyl, 31.6, 29.6, 21.2
(CH2), 12.6 (CH3).
FABMS (m/e) data are as follows. 1b, found (calcd for
C
22H25ClN2OPd - Cl): 423 (423). 2b, found (calcd for C22H25-
BrN2OPd - Br): 423 (423). 3a , found (calcd for C19H17ClN2-
OPd - Cl): 395 (395). 3b, found (calcd for C23H25ClN2OPd -
Cl): 451 (452). 4a , found (calcd for C24H19ClN2OPd - Cl): 457
(457). 5a , found (calcd for C21H21ClN2OPd - Cl): 423 (423).
8b, found (calcd for C17H31ClN2OPd - Cl): 385 (385).
Anal. 14, found (calcd for C18H17N2BF4Pd): C, 47.30 (47.56);
H, 3.94 (3.77); N, 6.05 (6.16).
MALDIMS (m/e) data are as follows. 7b, found (calcd for
40H37ClN2O3Pd - Cl): 700 (700).
C
FABMS (m/e) data are as follows. 13, found (calcd for
Compound 9b could not be characterized by FD-, FAB- or
C
C
C
19H17N2O3F3SPd - CF3SO3): 367 (367). 15, found (calcd for
18H31F3N2O4SPd - CF3SO3): 386 (385). 16, found (calcd for
19H27F3N2O4SPd - CF3SO3): 394 (393).
MALDIMS measurements due to fast fragmentations during
the measurements.
Syn t h esis of [(8-(2-p yr id yl)q u in olin e)(η3-C3H 5)p a lla -
d iu m (II)]OTf, [(8-P Q)P d (η3-C3H5)](OTf) (12). [Pd(η3-C3H5)-
Cl]2 (100 mg; 0.27 mmol), 8-PQ (62 mg; 0.30 mmol), and NaOTf
(244 mg; 1.37) were dissolved in dichloromethane (20 mL) and
stirred for 1 h. The suspension was filtered and the solvent
Cr ysta l Str u ctu r e Deter m in a tion of 1a . Numerical data
on the structure determination have been collected in Table
1. X-ray data were collected for a yellowish crystal glued on
top of a glass fiber and transferred into a cold nitrogens tream