S. Kolay et al. / Journal of Organometallic Chemistry 794 (2015) 40e47
45
Found: C, 43.64; H, 4.87%. 1H NMR (CDCl3)
d
: 2.24 (s, 4-Me); 2.61 (s,
Table 4
Selected bond length (Å) and angles (ꢁ) for [PtCl{(CH2C6H2Me2-4,6)TeMes}(PPh3)]
2,6-Me); 6.85 (s, 3,5-CH). 13C{1H} NMR (CDCl3)
d: 20.9, 26.8, 116.8
(4).
(TeeC), 129.3 (3,5-CH), 139.8, 143.6. 125Te{1H} NMR (CDCl3)
d
: 467
(1J(195Pte125Te) ¼ 379 Hz) ppm. 195Pt{1H} NMR (CDCl3)
d
: ꢀ3449
Pt1eP1
Pt1eCl2
Pt1eTe1
Pt1eC7
Te1eC1
Te1eC10
P1ePt1eCl2
P1ePt1eTe1
P1ePt1eC7
Cl2ePt1eTe1
Cl2ePt1eC7
Te1ePt1eC7
Pt1eC7eC2
Pt1eTe1eC1
Pt1eTe1eC10
C1eTe1eC10
2.268(4)
2.412(5)
2.5504(11)
2.029(14)
2.080(17)
2.161(17)
94.49(15)
175.50(11)
91.8(4)
Pt2eP2
Pt2eCl1
Pt2eTe2
Pt2eC43
Te2eC37
Te2eC46
P2ePt2eCl1
P2ePt2eTe2
P2ePt2eC43
Cl1ePt2eTe2
Cl1ePt2eC43
Te2ePt2eC43
Pt2eC43eC38
Pt2eTe2eC37
Pt2eTe2eC46
C37eTe2eC46
2.273(4)
2.410(5)
2.5410(12)
2.09(2)
2.15(2)
2.13(2)
91.07(17)
177.37(12)
94.8(5)
(1J(195Pte125Te) ¼ 359 Hz) ppm.
6.4. trans-[PtCl2(PhTeMes)2] (1d)
Prepared
similar
to
1a
and
recrystallized
from
dichloromethane-hexane in 75% yield as orange crystals; m. p.
198 ꢁC (dec). Anal. calcd. for C30H32Cl2PtTe2: C, 39.43; H, 3.53%.
86.25(11)
173.4(5)
87.6(4)
86.35(13)
174.0(5)
87.8(4)
Found: C, 39.07; H, 3.45%. 1H NMR (CDCl3)
d: 2.29 (s, 4-Me), 2.68 (s,
2,6-Me); 6.96 (s, 3,5-CH); 7.30 (br, m); 7.59 (br) (Ph). 125Te{1H} NMR
119.2(10)
92.5(5)
119.1(12)
93.0(4)
(CDCl3)
d
: 575 (1J(195Pte125Te) ¼ 366 Hz), 576 (1J(PteTe) ¼ 369 Hz)
ppm. 195Pt{1H} NMR (CDCl3)
d
: ꢀ3555, ꢀ3557 ppm.
104.2(4)
102.2(7)
107.7(4)
103.0(7)
6.5. trans-[PtCl2(o-tolTeMes)2] (1e)
distilled water and dried over anhydrous Na2SO4. The clear solution
Prepared similar to 1a
and
recrystallized
from
was passed through Cellite and concentrated to 5 ml. The title
dichloromethane-hexane in 70% yield as orange crystals; m. p. >
200 ꢁC. Anal. calcd. for C32H36Cl2PtTe2: C, 40.81; H, 3.85%. Found:
complex was precipitated as
a greenish yellow powder by
C,40.65; H, 3.78%. 1H NMR (CDCl3)
d: 2.29, 2.30 (each s, 4-Me of
Mes), 2.45, 2.48 (each s, 2-Me of tol); 2.72, 2.74 (each s, 2,6-Me of
addition of hexane and then was washed with hexane and
diethyl ether and dried, (Yield: 123 mg, 61%), m.p. 196 ꢁC (dec).
Anal. calcd. for C24H20Cl2PtTe2: C, 34.75; H, 2.42%. Found: C, 34.31;
Mes); 6.95, 6.97 (each s, 3,5-CH of Mes); 7.02e7.22 (m, tol); 7.51,
H, 2.40%. 1H NMR (CDCl3)
d: 7.22e7.27 (m), 7.35e7.40 (m),
7.64 (each d, 7.8 Hz, tol) ppm. 125Te{1H} NMR (CDCl3)
d
: 541; 543
515 Hz) ppm. 195Pt{1H} NMR (CDCl3)
: ꢀ3611, ꢀ3615 ppm.
7.61e7.64 (m) [Ph] ppm. 125Te{1H} NMR (CDCl3)
d: 717 (major,
(1J(195Pte125Te)
¼
1J(195Pte125Te) ¼ 1329 Hz) and 728 (minor) ppm. 195Pt{1H} NMR
d
(CDCl3)
d
: ꢀ3650 (major), ꢀ3653 (minor). When a CDCl3 solution of
the complex is left for longer duration of acquisition additional
peaks in the 125Te{1H} and 195Pt{1H} NMR spectra were observed
which could be due to dissociation in solution.
6.6. [PtCl{(CH2C6H2Me2-4,6)TeMes}(TeMes2)] (2)
A THF (~25 ml) solution of trans-[PtCl2(TeMes2)2] (60 mg,
0.06 mmol) was refluxed with stirring for 2 h under an argon at-
mosphere whereupon the initial orange colour faded. After cooling
the solution, the solvent was evaporated under reduced pressure to
give a yellow residue which was washed with hexane and recrys-
tallized from dichloromethane-hexane mixture as red prismatic
crystals (Yield: 40 mg, 70%); m.p. 182 ꢁC (dec). Anal. calcd. for
6.2. trans-[PtCl2{(Te(tol-o)2}2] (1b)
Prepared similar to 1a and recrystallized from dichlor-
omethaneehexane as yellow needles (Yield: 155 mg, 73%); m. p.
>210 ꢁC. Anal. calcd. for C28H28Cl2PtTe2: C, 37.97; H, 3.19%, Found:
C, 37.23; H, 3.16.%. 1H NMR (CDCl3)
d: 2.25, 2.56 (each s); 7.08e7.15
C
36H43ClPtTe2: C, 44.97; H, 4.51%. Found: C, 45.02; H, 4.61%. 1H NMR
(CDCl3) : 2.02, 2.19, 2.24, 2.27, 2.34, 2.53 (each s for Me); 4.0
(m), 7.24e7.36 (m); 7.79 (dd, 1.2, 7.5 Hz); 7.88 (d,d, 1.2, 7.5 Hz)
d
ppm. 125Te{1H} NMR (CDCl3)
d
: 622 (1J(195Pte125Te) ¼ 793 Hz)
(JAX ¼ 16.8, DnAX ¼ 105.8 Hz; metalated CH2); 6.66 (s, 4,6-CH of Mes
ppm; when this solution was left for overnight
additional peak appeared in 125Te NMR spectrumat
a
new
605
of metalated); 6.71 (s, 4,6-CH, Mes2Te); 6.86, 7.04 (CH of metalated
ring) ppm.125Te{1H} NMR (CDCl3)
d
: 336 (1J(195Pte125Te) ¼ 612 Hz);
d:
(1J(195Pte125Te) ¼ 1357 Hz) ppm while 195Pt{1H} NMR (CDCl3)
592 (1J(195Pte125Te)
¼
1528 Hz) ppm; for the dimer: 424
(1J(195Pte125Te) ¼ 788 Hz) and 600 (1J(195Pte125Te) ¼ 1192 Hz);
showed two resonances at
d
: ꢀ3717, ꢀ4324 ppm.
260(s, TeMes2) ppm. 195Pt{1H} NMR (CDCl3)
d
:
ꢀ4286
(minor); ꢀ4450 (major).
6.3. trans-[PtCl2(TeMes2)2] (1c)
Prepared similar to
1a
and
recrystallized
from
6.7. [PtCl{(CH2C6H2Me2-4,6)TeMes}(PPh3)] (4)
dichloromethane-hexane in 64% yield as light orange crystalline
solid; m.p.180 ꢁC. Anal. calcd. for C36H44Cl2PtTe2: C, 43.33; H, 4.44%.
To a dichloromethane solution of 2 (45 mg, 0.047 mmol) a
Table 5
Secondary CeH … M interactions with the metal centre (Å/ꢁ)a.
trans-PtCl2(PhTeMes)2 (1d)
trans-PtCl2(o-tolTeMes)2 (1e)
trans-PtCl2(TeMes2)2 (1c)
Molecule A
Molecule B
C7eH7c … Pt1
:C7eH7c-Pt1
Pt1eTe1eC1eC2
Pt1eCl1
:Cl1ePt1eCl2
Pt1eTe1
3.114
157.06
ꢀ58.31
2.286
180
2.850
119.37
31.47
2.309
180
2.794
122.89
1.58
2.320
179.06
2.572
2.689
134.74
ꢀ2.74
2.289
174.08
2.579
2.578
180
2.577
180
:Te1ePt1eTe2
Mean sq. plane-M
166.41
0.042
168.39
0.180
a
The distances have been noted down using mercury program, hence do not have esds.