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J.T. Hoffman, C.J. Carrano / Inorganica Chimica Acta 359 (2006) 1248–1254
2.3. [(L2)Zn(SC6H5)] (3)
(q, J = 319 Hz, –CF3), 107.39, 90.08, 71.77, 54.85, 13.98,
11.27.
Thiophenol (220 lL, 2.15 mmol) was added to a solu-
tion of (2) (1.0 g, 2.15 mmol) in 50 mL anhydrous CH2Cl2
under inert atmosphere with a gastight syringe. After stir-
ring for 1 h the solution was reduced to dryness and
brought into the dry box. The crude product was dissolved
in anhydrous CH2Cl2, and passed through a plug of Celite.
The filtered solution was reduced to dryness to yield
916 mg (76.1% yield) of white crystalline product. X-ray
quality crystals of [(L2)Zn(SC6H5)] were grown by layering
a concentrated solution of CH2Cl2 with hexanes. Anal.
Calc. for [(L2)Zn(SC6H5)], C32H33N5O2SZn Æ (CH2-
Cl2)2 Æ H2O: C, 64.34; H, 5.40; N, 10.00. Found: C, 65.06;
H, 5.63; N, 10.24%. 1H NMR (CDCl3) d 7.68 (d, 2H,
SArH), 7.61 (d, 4H, ArH), 7.22 (m, 4H, ArH), 7.15 (m,
2H, ArH), 7.10 (m, 2H, SArH), 6.97 (t, 1H, SArH), 6.62
(s, 1H, –CH–), 5.69 (s, 2H, PzH), 2.13 (s, 6H, Pz–CH3),
2.02 (s, 6H, Pz–CH3). 13C NMR (CDCl3) d 149.68,
146.30, 141.17, 140.87, 132.41, 128.09, 127.39, 126.82,
126.31, 122.46, 105.53, 84.50, 70.81, 12.62, 10.71.
2.6. ½ðL2OCH3ÞZnIðH2OÞꢁþBF (6)
ꢀ
4
Compound was synthesized by the same method as for
(5) using (4) (80 mg, 0.11 mmol) and AgBF4 (20.3 mg,
0.104 mmol). X-ray quality crystals were made by layering
a concentrated solution of CH2Cl2 with diisopropyl ether.
Transparent cluster shaped crystals were formed within
1
24 h. 103 mg (48.4% yield) H NMR (CDCl3) d 7.36 (dd,
4H, ArH), 7.35 (m, 2H, ArH), 7.08 (m, 4H, ArH), 6.30
(s, 1H, –CH–), 5.88 (s, 2H, PzH), 3.21 (s, 3H, Pz–CH3),
2.53 (s, 6H, Pz–CH3), 1.94 (s, 6 H, Pz–CH3). 13C NMR
(CDCl3) d 153.19, 144.74, 133.54, 129.51, 128.63, 128.59,
107.48, 90.78, 71.64, 55.31, 13.93, 11.21.
2.7. X-ray crystallography
Crystals of complexes 1–6 were sealed in thin-walled
quartz capillaries or nylon loops (Hampton Research),
and mounted on either a Bruker SMART or X8 APEX
CCD diffractometer. The structures were solved using
direct methods or via the Patterson function, completed
by subsequent difference Fourier syntheses, and refined
by full-matrix least-squares procedures on F2. All non-
hydrogen atoms were refined with anisotropic displacement
coefficients and treated as idealized contributions using a
riding model except where noted. All software and sources
of the scattering factors are contained in the SHELXTL 5.0
program library (G. Sheldrick, Siemens XRD, Madison,
WI). Crystallographic data collection parameters are given
in Table 1, while selected bond lengths and angles for the
complexes 1–3 are shown in Table 2 and for 4–6 in Table
3. The ORTEP diagram for [(L2)ZnI] is shown in Fig. 1;
for [(L2)ZnCH3] in Fig. 2; for [(L2)ZnSPh] in Fig. 3;
[(L2OCH3)ZnI2] in Fig. 4; [(L2OCH3)ZnI(Tf)] in Fig. 5
2.4. [(L2OCH3)ZnI2] (4)
To a stirring solution of (1) (130 mg, 0.23 mmol) in
30 mL of anhydrous CH3CN under argon was added
MeI (140 lL, 2.59 mmol) with a gas-tight syringe. The
resulting solution was refluxed under argon for 20 h. The
resulting pale yellow solution was reduced to dryness.
The yellow crude product was taken into the dry box, dis-
solved in anhydrous CH2Cl2, and passed through a plug of
Celite. The solvent of the filtered solution was removed by
reduced pressure to yield 0.140 g (86.5% yield) of pale yel-
low product. X-ray quality crystals of [(L2OCH3)ZnI2]
were grown from a 1:2 solution of concentrated solution
in CH2Cl2 and diisopropyl ether. 1H NMR (CDCl3) d
7.27 (dd, 4H, ArH), 7.21 (m, 2H, ArH), 7.04 (m, 4H,
ArH), 6.08 (s, 1H, –CH–), 5.72 (s, 2H, PzH), 3.04 (s, 3H,
–OCH3), 2.59 (s, 6H, Pz–CH3), 1.74 (s, 6H, Pz–CH3). 13C
NMR (CDCl3) d 154.08, 143.76, 134.40, 129.08, 128.90,
128.33, 107.60, 89.53, 72.43, 54.76, 15.26, 11.38.
and ½ðL2OCH3ÞZnIðH2OÞꢁþBF in Fig. 6.
ꢀ
4
2.8. Physical methods
1H and 13C NMR spectra were collected on Varian 200,
300 or 500 MHz NMR spectrometers. Chemical shifts are
reported in ppm relative to an internal standard of TMS.
The 13C quaternary carbon peaks that are not observed
are a result of either poor solubility and/or overlapping sig-
nals. IR spectra were recorded as KBr disks on a Ther-
moNicolet Nexus 670 FT-IR spectrometer and are
reported in wavenumbers.
2.5. [(L2OCH3)ZnI(Tf)] (5)
To a stirring solution of (4) (80 mg, 0.11 mmol) in
30 mL of anhydrous CH2Cl2 under argon was added AgTf
(28.5 mg, 0.11 mmol). The resulting solution was stirred
under argon for 20 h. The resulting pale yellow solution
was filtered to remove AgI and reduced to dryness. The
pale yellow crude product was dissolved in anhydrous
CH2Cl2, and layered with diisopropyl ether. Transparent
block shaped crystals were formed within 24 h. 48 mg
2.9. Kinetic experiments
1
(58.2% yield). H NMR (CDCl3) d 7.35 (m, 2H, ArH),
All experiments were performed under pseudo-first-
order conditions with the alkylating agent in large excess.
In a typical experiment, 1.8 · 10ꢀ5 mol of the metal com-
plex was dissolved in 1 mL of solvent to give an 18 mM
solution. The solution of the metal complex was then trans-
7.33 (m, 4H, ArH), 7.07 (m, 4H, ArH), 6.18 (s, 1H, –
CH–), 5.85 (s, 2H, PzH), 3.16 (s, 3H, –OCH3), 2.56 (s,
6H, Pz–CH3), 1.88 (s, 6H, Pz–CH3). 13C NMR (CDCl3)
d 153.70, 143.86, 133.90, 129.35, 128.66, 128.51, 119.79