Reactivity of Platina-â-diketones
Organometallics, Vol. 21, No. 21, 2002 4375
Ta ble 6. Cr ysta l Da ta a n d Str u ctu r e Refin em en t Deta ils for 2a , 2b‚CDCl3, a n d 4d
2a
2b‚CDCl3
4d
empirical formula
fw
cryst syst
space group
C
14H26N2O2Pt
C19H19Cl4DN2OPt
630.27
monoclinic
P21/n
C14H27ClN2O2Pt
485.92
orthorhombic
Pbca
449.46
monoclinic
P21/n
a, Å
b, Å
c, Å
9.0874(19)
16.994(7)
10.755(2)
99.72(2)
1637.0(8)
4
1.824
8.572
872
13.903(3)
8.889(1)
18.174(5)
98.38(3)
2222.1(8)
4
1.884
6.807
11.044(2)
11.875(3)
26.348(5)
â, deg
V, Å3
3455(1)
8
1.868
8.279
Z
F(calcd), g cm-3
µ(Mo KR), mm-1
F(000)
1208
1888
scan range, deg
recip lattice segments h,k,l
2.57 < θ < 26.04
-10 to +10, -20 to +20,
-13 to +13
2.56 < θ < 26.06
-17 to +16, -9 to +10,
-22 to +22
2.41 < θ < 26.08
-13 to +13, -14 to +14,
-31 to +32
no. of rflns collected
no. of indep rflns
12 458
12 135
24 187
3035 (R(int) ) 0.0623)
276
1.113
R1 ) 0.0184, wR2 ) 0.0430
R1 ) 0.0223, wR2 ) 0.0475
1.154 and -0.541
4276 (R(int) ) 0.0623)
324
1.087
R1 ) 0.0315, wR2 ) 0.0750
R1 ) 0.0409, wR2 ) 0.0827
1.385 and -1.260
3363 (R(int) ) 0.1020)
284
1.109
R1 ) 0.0430, wR2 ) 0.0906
R1 ) 0.0667, wR2 ) 0.1001
1.521 and -0.914
no. of params refined
goodness of fit on F2
final R (I > 2σ(I))
R, all data
largest diff peak and hole, e Å-3
1.51 (m, 4H, 2 × CH2, n-Pr), 2.05 (s, 6H, 2 × NCCH3), 2.17 (s
CH, i-Pr), 143.6 (s, N(H)-CHd), 180.4 (s, NC(O)CH3), 202.1
(s + d, J Pt,C ) 1072.4 Hz, PtC(O)CH3).
3
1
+ d, 6H, J Pt,H ) 19.5 Hz, 2 × COCH3), 3.76 (t, 4H, 2 × CH2,
n-Pr). 13C NMR (CDCl3, 101 MHz): δ 11.2 (s, 2 × CH3, n-Pr),
17.8 (s, 2 × NCCH3), 22.6 (s, 2 × CH2, n-Pr), 43.6 (s, 2 ×
COCH3), 56.0 (s, 2 × CH2, n-Pr), 172.1 (s, 2 × NCCH3), 231.6
(s, 2 × COCH3).
Data for complex 4c (R ) c-Hex) are as follows. Yield: 144.5
1
mg (84%). H NMR (CDCl3, 500 MHz): δ 1.04-2.12 (m, 20H,
CH2, c-Hex), 2.25 (s, 3H, NC(O)CH3), 2.30 (s, 3H, PtC(O)CH3),
3.43 (br, 1H, CH, c-Hex), 3.71 (br, 1H, CH, c-Hex), 4.76 (br,
1H, N-CHd), 7.1/7.4 (br/br, 1H/1H, N(H)-CHd/NH). 13C
NMR (CDCl3, 101 MHz): δ 22.1 (s, NC(O)CH3), [24.5, 24.6,
24.9, 25.2, 25.4, 25.5, 30.7, 31.2, 32.9 (s, CH2, c-Hex)], 42.1 (s
Data for complex 2b are as follows. Yield: 65.2 mg (40%).
1H NMR (CDCl3, 400 MHz): δ 1.62 (s, 3H, NCCH3), 1.88 (s,
3H, NCCH3), 2.13 (s, 3H, COCH3), 7.06 (m, 4H, HPh), 7.29 (m,
2H, HPh), 7.43 (m, 4H, HPh). 13C NMR (CDCl3, 101 MHz): δ
1
3
+ d, J Pt,C ) 152.2 Hz, PtC(O)CH3), 51.7 (s + d, J Pt,C ) 475.8
Hz, N-CHd), 57.5 (s, NCH, c-Hex), 59.8 (s, NCH, c-Hex), 143.1
(s, N(H)CHd), 180.5 (s, NC(O)CH3), 202.0 (s, PtC(O)CH3).
3
19.7 (s, NCCH3), 21.1 (s, NCCH3), 39.7 (s + d, J Pt,C ) 101.7
Hz, COCH3), [121.7, 122.2, 127.5, 128.2, 128.8, 129.6 (s, CPh)],
145.0 (s, i-CPh), 148.2 (s, i-CPh), 172.8 (s, NCCH3), 173.5 (s,
NCCH3), 213.8 (s, COCH3).
Data for complex 4d (R ) t-Bu) are as follows. Yield: 94.9
mg (61%). 1H NMR (CDCl3, 400 MHz): δ 1.43 (s, 9H, CH3,
[P t(COMe)Cl{RN(H)CHdCHN(R)C(O)Me}] (4). At -40
°C, to [Pt2{(COMe)2H}2(µ-Cl)2] (1a ; 100 mg, 0.16 mmol) in thf
(5 mL) was added RNdCHCHdNR (0.32 mmol) as a solid (R
) c-Hex, t-Bu) or as a solution (R ) n-Pr, i-Pr) in thf (0.5-1
mL). The reaction mixture was warmed to room temperature
over 20 min and then stirred for another 10 min, yielding a
clear, nearly colorless solution. About half of the solvent was
evaporated in vacuo. Addition of diethyl ether (15-20 mL)
resulted in a white precipitate of the product that was filtered
off, washed with diethyl ether, and dried briefly in vacuo.
Data for complex 4a (R ) n-Pr) are as follows. Yield: 65.9
mg (45%). 1H NMR (CDCl3, 400 MHz): δ 0.91 (t, 3H, CH3,
n-Pr), 0.93 (t, 3H, CH3, n-Pr), 1.54 (m, 1H, CHH, n-Pr), 1.72
(m, 3H, 3 × CHH, n-Pr), 2.25 (s, 3H, PtC(O)CH3), 2.28 (s, 3H,
NC(O)CH3), 3.00 (m, 1H, CHH, n-Pr), 3.24 (m, 1H, CHH, n-Pr),
3.55 (m, 1H, CHH, n-Pr), 3.69 (m, 1H, CHH, n-Pr), 4.92 (s+d,
t-Bu), 1.51 (s, 9H, CH3, t-Bu), 2.29 (s, 3H, PtC(O)CH3), 2.39
2
(s, 3H, NC(O)CH3), 4.3 (d, 1H, NH), 5.04 (s + d, 1H, J Pt,H
)
113.1 Hz, N-CHd), 7.0 (m, 1H, N(H)-CHd). 13C NMR (CDCl3,
101 MHz): δ 25.1 (s, NC(O)CH3), 29.1 (s, CH3, t-Bu), 30.4 (s,
CH3, t-Bu), 41.5 (s + d, 2J Pt,C ) 138.4 Hz, PtC(O)CH3), 54.8 (s,
1
C, t-Bu), 59.0 (s, C, t-Bu), 59.2 (s + d, J Pt,C ) 393.7 Hz,
N-CHd), 127.8 (s, N(H)-CHd), 181.7 (s, NC(O)CH3), 201.1
1
(s + d, J Pt,C ) 1075.1 Hz, PtC(O)CH3).
X-r a y Cr ysta llogr a p h y. Crystals suitable for X-ray dif-
fraction analyses were grown from CDCl3 solution (2a , 2b‚
CDCl3) or by slow addition of diethyl ether to a dilute thf
solution (4d ). Intensity data were collected on a Stoe IPDS
diffractometer with Mo KR radiation (λ ) 0.71073 Å, graphite
monochromator) at 220(2) K. A summary of the crystal-
lographic data, the data collection parameters, and the refine-
ment parameters is given in Table 6. Absorption correction
was applied numerically (Tmin/Tmax 0.14/0.36 (2a ), 0.34/0.71
(2b‚CDCl3), 0.35/0.45 (4d )). The structures were solved by
direct methods with SHELXS-8615 and refined using full-
matrix least-squares routines against F2 with SHELXL-93.15
Non-hydrogen atoms were refined with anisotropic displace-
ment parameters. All H atoms except for H1 in complex 4d
were found in the difference Fourier map and refined isotro-
pically. Hydrogen atom H27 of 4d was refined with the
isotropic displacement parameter Ueq ) 0.08. The hydrogen
atom H1 in 4d was included in a calculated position and
refined with an isotropic displacement parameter according
to the riding model.
2
1H, J Pt,H ) 138.9 Hz, N-CHd), 7.5 (m, 1H, N(H)CHd), 8.7
(br, 1H, NH). 13C NMR (CDCl3, 125 MHz): δ 11.1 (s, CH3,
n-Pr), 11.2 (s, CH3, n-Pr), 21.3 (s, 2 × CH2, n-Pr), 22.2 (s, NC-
(O)CH3), 42.8 (s+d, 2J Pt,C ) 141.6 Hz, PtC(O)CH3), 52.1 (s, CH2,
n-Pr), 52.2 (s, CH2, n-Pr), 53.7 (s, N-CHd), 157.3 (s, N(H)-
1
CHd), 181.2 (s, NC(O)CH3), 204.1 (s + d, J Pt,C ) 1121.1 Hz,
PtC(O)CH3).
Data for complex 4b (R ) i-Pr) are as follows. Yield: 128.8
mg (88%). 1H NMR (CDCl3, 400 MHz): δ 1.15 (d, 3H, CH3,
i-Pr), 1.21 (d, 3H, CH3, i-Pr), 1.33 (d, 3H, CH3, i-Pr), 1.36 (d,
3H, CH3, i-Pr), 2.26 (s, 3H, NC(O)CH3), 2.30 (s, 3H, PtC(O)-
CH3), 3.84 (br, 1H, N-CH, i-Pr), 4.12 (br, 1H, N(H)-CH, i-Pr),
4.71 (br, 1H, N-CHd), 7.3/7.4 (br/br, 1H/1H, NH/N(H)-
CHd). 13C NMR (CDCl3, 101 MHz): δ 20.1 (s, CH3, i-Pr), 20.5
(s, CH3, i-Pr), 20.7 (s, CH3, i-Pr), 22.2 (s, CH3, i-Pr), 22.6 (s,
(15) Sheldrick, G. M. SHELXS-86 and SHELXS-93: Programs for
Crystal Structure Determination; University of Go¨ttingen, Go¨ttingen,
Germany, 1986 and 1993.
2
NC(O)CH3), 42.1 (s + d, J Pt,C ) 147.5 Hz, PtC(O)CH3), 50.2
1
(s + d, J Pt,C ) 480.5 Hz, N-CHd), 50.4 (s, CH, i-Pr), 51.4 (s,