5530 Organometallics, Vol. 20, No. 26, 2001
Ru¨ther et al.
[P d Cl(CH3){σ2(N,N)-tr is(N-m eth ylim id a zol-2-yl)m eth -
oxym eth a n e}] (1a ). Anal. Calcd for C15H21N6OClPd: C,
40.64; H, 4.78; N, 18.96. Found: C, 40.43; H, 4.59; N, 18.94.
MS (LSIMS): m/z 407, [M - Cl]+ (34%); 392 [M - Cl, CH3]+
(71%); 255 [Ligand - OCH3]+ (100%). 1H NMR (200 MHz,
CDCl3): δ 7.96 (d, J ) 1.4 Hz, 1H, Imd H), 7.30 (d, J ) 1.6
Hz, 1H, Imd H), 7.06 (s, 1H, Imd H), 6.99 (d, J ) 1.6 Hz, 1H,
Imd H), 6.92 (d, J ) 1.4 Hz, 1H, Imd H), 6.84 (s, 1H, Imd H),
3.67 (s, 3H, NCH3), 3.54 (s, 3H, NCH3), 3.38 (s, 3H, NCH3),
3.06 (s, 3H, OCH3), 0.91 (s, 3H, Pd(CH3)).
[P d (CH3){σ3(N,N,N)-tr is(N-m eth ylim id a zol-2-yl)m eth -
oxym eth a n e}]2[Cl]2 (1a ′). This complex was prepared in a
manner analogous to that described for 1a , using 42.8 mg
(0.161 mmol) of [PdCl(CH3)(COD)] and 46.2 mg (0.161 mmol)
of (mim)COCH3 in methanol. The resulting slightly yellow
solid was washed with CH2Cl2 (3 × 1.5 mL) and dried under
vacuum. Yield: 65 mg (92%).
[P d (CH 3){σ3(N,N,N)-t r is(1-m et h ylim id a zol-2-yl)m et h -
oxym eth a n e}]2[BF 4]2 (1b). 1a (84 mg, 0.19 mmol) and AgBF4
(36.9 mg, 0.19 mmol) were mixed as solids, and a 1:1 mixture
of CH3CN and CH2Cl2 (5 mL) was added with stirring. A white
precipitate (AgCl) formed. The mixture was stirred for 1 h,
after which time it was filtered through a small bed of Celite.
The solvent was removed in vacuo, and the residue was
washed with Et2O (2 × 4 mL) and dried in vacuo to afford an
off-white solid. Yield: 89.3 mg (95%). Anal. Calcd for C30H42
-
N
12B2F8Pd2: C, 36.42; H, 4.29; N, 16.99. Found: C, 35.96; H,
4.56; N, 16.84. MS (electrospray): m/z 901, [M - BF4]+ (38%);
814, [M - 2BF4]2+ (100%). 1H NMR (200 MHz, CD3CN): δ 7.67
(d, J ) 1.6 Hz, 1H, Imd H), 7.50 (d, J ) 1.6 Hz, 1H, Imd H),
7.28 (d, J ) 1.6 Hz, 1H, Imd H), 7.18 (d, J ) 1.6 Hz, 1H, Imd
H), 6.93 (d, J ) 1.4 Hz, 1H, Imd H), 5.58 (d, J ) 1.4 Hz, 1H,
Imd H), 4.38 (s, 3H, NCH3), 3.62 (s, 3H, NCH3), 3.61 (s, 3H,
NCH3), 2.82 (s, 3H, OCH3), -0.24 (s, 3H, Pd(CH3)).
Alternatively, 1a ′ can be prepared by dissolving 1a (7 mg)
in CH3OH (1.5 mL). After the mixture was stirred for ca. 3 h
at room temperature, the solvent was removed in vacuo and
the remaining solid washed with Et2O (2 × 1.5 mL). Drying
under vacuum afforded an off-white solid. Yield: 7 mg (100%).
Anal. Calcd for C30H42N12O2Cl2Pd2‚CH2Cl2: C, 38.32; H,
4.57; N, 17.31. Found: C, 38.68; H, 4.60; N, 17.69. MS
(electrospray): m/z 849, [M - Cl]+ (14%); 814, [M - 2Cl]2+
[P d (CH3){σ2(N,N)-4,4-d im eth yl-1,1-bis(1-m eth ylim id a -
zol-2-yl)p en t a n -3-on e}(CH 3CN)][BF 4] (3b). This complex
was prepared in a manner analogous to that described for 1b,
using 56.6 mg (0.108 mmol) of 3a and 21 mg (0.108 mmol) of
AgBF4. A light yellow solid was obtained. Yield: 54 mg (95%).
Anal. Calcd for C18H28N5OBF4Pd: C, 41.28; H, 5.40; N, 13.38.
Found: C, 38.95; H, 5.89; N, 12.23. MS (LSIMS): m/z 901, [M
- BF4]+ (19%); 395, [(Ligand)Pd(CH3)]+ (39%); 380, [(Ligand)-
Pd]+ (100%); 361, [(Ligand)Pd - OCH3]+ (52%); 275, [Ligand
1
(100%). H NMR (400 MHz, CD3OD): δ 7.65 (d, J ) 1.6 Hz,
1
+ H]+ (94%). H NMR (200 MHz, CDCl3): δ 6.95 (s, 1H, Imd
1H, Imd H), 7.53 (d, J ) 1.6 Hz, 1H, Imd H), 7.33 (d, J ) 1.6
Hz, 1H, Imd H), 7.13 (d, J ) 1.6 Hz, 1H, Imd H), 6.99 (d, J )
1.3 Hz, 1H, Imd H), 5.59 (d, J ) 1.3 Hz, 1H, Imd H), 4.37 (s,
3H, NCH3), 3.62 (s, 3H, NCH3), 3.59 (s, 3H, NCH3), 2.77 (s,
3H, OCH3), -0.28 (s, 3H, Pd(CH3)). 13C NMR (400 MHz, CD3-
OD): δ 142.7 (ring 3), 142.2 (ring 2), 140.0 (ring 1) (C dN);
132.0 (ring 2), 127.2 (ring 3), 124.5 (ring 1) (C4); 128.0 (ring
2), 127.9 (ring 1), 126.8 (ring 3) (C5); 81.3 (COCH3); 52.8
(COCH3); 39.9 (ring 2), 36.0 (ring 3), 35.5 (ring 1) (N-CH3);
-3.1 (Pd-CH3).
H), 6.93 (s, 1H, Imd H), 6.88 (s, 1H, Imd H), 6.85 (s, 1H, Imd
3
2
H), 4.86 (d/d, J ) 8.3/5.5 Hz, 1H, CH), 4.12 (d/d, J ) 18 Hz,
3J ) 8.3 Hz, 1H, CH2), 3.93 (s, 3H, NCH3), 3.83 (s, 3H, NCH3),
3.42 (d/d, 2J ) 18 Hz, 3J ) 5.5 Hz, 1H, CH2), 2.47 (s, 3 H,
CH3CN), 1.08 (s, 9H, t-Bu), 0.79 (s, 3H, Pd(CH3)). IR (KBr):
1702 (νCO).
X-r a y Da ta Collection a n d Str u ctu r e Refin em en t for
Com p lexes 1b,c. Crystals of 1b suitable for X-ray diffraction
have been obtained by cooling a CD3OD solution of the crude
reaction product at -20 °C. Crystals of 1c suitable for X-ray
diffraction formed when a CDCl3 solution of 1a was allowed
to stand for 4 days at room temperature.
[P d Cl(CH3){σ2(N,P )-2-[2-(d ip h en ylp h osp h in o)-1-(1-m e-
t h ylim id a zol-2-yl)et h yl]-1-m et h ylim id a zole}] (2a ).7 1H
NMR (400 MHz, CDCl3): δ 7.66 (s (br), 2H, phenyl) 7.57 (s
(br, 2H, phenyl), 7.4 (s (br), 7H, 6 phenyl + 1 Imd H), 6.88 (s
(br), 2H, ImH), 6.42 (s (br), 1H, Im H), 5.46 (m (br), 1H, CH),
Full spheres of CCD area-detector diffractometer data were
measured (T ca. 153 K; ω-scans; monochromatic Mo KR
radiation, λ ) 0.710 73 Å; Bruker AXS instrument), yielding
3.60 (m (br), 1H, CH2), 3.28 (s (br), 3H, N-CH3), 3.16 (s (br),
3
3H, N-CH3), 2.95 (m (br), 1H, CH2), 0.61 (d (br), 3H, J P-H
)
N
(total) reflections, merging to Nunique (Rint quoted) after “empiri-
3.2 Hz, Pd-CH3). 31P NMR (400 MHz, CD2Cl2): δ 29.4 (s (br).
[P d (CH3){σ3(N,N,P )-2-[2-(d ip h en ylp h osp h in o)-1-(1-m e-
th ylim id a zol-2-yl)eth yl]-1-m eth ylim id a zole}]2[Cl]2 (2a ′).
1H NMR (200 MHz, CD3OD): δ 7.58 (m, 4H, phenyl), 7.48 (m,
7H, 6 phenyl + 1 Imd H), 7.0 (d, J ) 1.5 Hz, 1H, Imd H), 4.63
(m, 1H, CH), 3.89 (s, 3H, NCH3), 3.24 (m, 2H, CH2), 3.19 (s,
3H, NCH3), -0.35 (d, 3J ) 3.3 Hz, 3H, Pd-CH3). 31P NMR
(400 MHz, CD3OD): δ 31.4 ppm.
cal”/multiscan absorption correction (proprietary software). No
(F > 4σ(F)) were used in the full-matrix least-squares refine-
ments, refining non-hydrogen atom anisotropic displacement
parameter forms and (x, y, z, Uiso
) constrained at estimated
H
values. Conventional residuals R and Rw (weights: (σ2(F) +
0.0004F2)-1) are quoted at convergence. Neutral atom complex
scattering factors were employed within the Xtal 3.7 program
system.22 Pertinent results are given below and in Figure 6
and Table 2, individual difficulties, variations in procedure,
and abnormalities being described as “variata”. In the figures,
50% amplitude displacement envelopes are shown for the non-
hydrogen atoms, hydrogen atoms as shown having arbitrary
radii of 0.1 Å.
[P d Cl(CH3){σ2(N,N)-4,4-d im eth yl-1,1-bis(1-m eth ylim i-
d a zol-2-yl)p en ta n -3-on e}] (3a ). Anal. Calcd for C16H25N4-
OClPd: C, 44.55; H, 5.85; N, 12.99. Found: C, 44.53; H, 5.88;
N, 12.74. MS (LSIMS): m/z 825, [2M - Cl]+ (19%); 669,
[(Ligand)2Pd(CH3)]+ (19%); 395, [M - Cl]+ (17%); 380, [M -
CH3 -Cl]+ (80%); 295, [M - Cl - CH3 - t-BuCO]+ (71%); 275,
[{LP d (Me/Cl)}2]Cl2‚4CHCl3 (1c): C33H43Cl15N12O2Pd2, Mr
) 1384.4, monoclinic, space group C2/c (C62h, No. 15), a )
14.3524(8) Å, b ) 13.5720(8) Å, c ) 26.310(2) Å, â )
91.765(1)°, V ) 5123 Å3, Dc(Z ) 4 dimers) ) 1.795 g cm-3, µMo
15.3 cm-1, specimen 0.14 × 0.19 × 0.05 mm, “T”min,max ) 0.76,
0.89, 2θmax ) 75°, Nt ) 49 468, N ) 12 932 (Rint ) 0.053), No
1
[LigandH]+ (90%); 189, [Ligand - t-BuCO]+ (100%). H NMR
(400 MHz, CDCl3; two isomers in a ca. 3.5:1 ratio (A:B)): δ
7.87 (d, J ) 1.6 Hz, 1H, Imd HB), 7.37 (d, J ) 1.2 Hz, 1H, Imd
HA), 7.31 (d, J ) 1.6 Hz, 1H, Imd HB), 7.03 (d, J ) 1.6 Hz, 1H,
Imd HA), 6.84 (d, J ) 1.6 Hz, 1H, Imd HB), 6.77 (d, J ) 1.2 Hz,
1H, Imd HA), 6.74 (d, J ) 1.6 Hz, 1H, Imd HA), 6.73 (d, J )
1.6 Hz, 1H, Imd HB), 4.80 (d/d, 3J ) 9/5 Hz, 1H, CHB), 4.75
) 8344, R ) 0.049, Rw ) 0.052, |∆Fmax| ) 1.5(1) e Å-3
.
Variata: as modeled in space group C2/c, the halves of the
dimer are related by a crystallographic 2-axis, implying
scrambling of the chloride and methyl entities between the
two sites at the two palladium atoms, attempted refinement
3
2
3
(d/d, J ) 9/5.2 Hz, 1H, CHA), 4.41 (d/d, J ) 17.6 Hz, J ) 9
Hz, 1H, C(HA)2), 4.22 (d/d, 2J ) 17.6 Hz, 3J ) 9 Hz, 1H, C(HB)2),
3.87 (s, 3H, NC(HB)3), 3.83 (s, 3H, NC(HA)3), 3.74 (s, 3H, NC-
2
3
(HB)3), 3.71 (s, 3H, NC(HA)3), 3.68 (d/d, J ) 17.6 Hz, J ) 5.2
Hz, 1H, C(HB)2), 3.34 (d/d, 2J ) 17.6 Hz, 3J ) 5.2 Hz, 1H,
C(HA)2), 1.11 (s, 3H, Pd(CH3)B), 1.10 (s, 9H, t-Bu), 1.05 (s, 9H,
t-BuA), 0.85 (s, 9H, Pd(CH3)A). IR (KBr): 1703 (νCO).
(22) The Xtal 3.7 System; Hall, S. R., du Boulay, D. J ., Olthof-
Hazekamp, R., Eds.; University of Western Australia: Nedlands, WA,
Australia, 2000.