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found: 237.1127; m/z calcd for C14H12N4Na: 259.0954 [M+Na]+;
found: 259.0947
(td, J=7.8, 1.5 Hz, 1H), 7.64 (dd, J=8.6, 1.9 Hz, 2H), 7.45–7.33 (m,
2H), 7.23–7.15 (m, 1H), 7.13 (t, J=2.2 Hz, 1H), 7.01 (dd, J=8.6,
2.5 Hz, 2H), 2.18 (d, J=2.8 Hz, 6H), 2.10 (s, 3H), 1.84 (s, 6H), 1.54
(s, 18H), 1.46 (s, 9H), 1.21 (s, 18H), 1.11 ppm (s, 9H); MS (ESI+,
MeOH): m/z calcd for C59H82N4O3PPt: 1120.5771 [M+H]+; found:
1120.5751; elemental analysis calcd (%) for C45H60N4O2PPt: C 63.25,
H 7.29, N 5.00; found: C 62.73, H 7.40, N 4.86.
2-(Benzo[d]oxazol-2-yl)phenol (HL5): This ligand was purchased
from Sigma–Aldrich and used without further purification.
2-(Benzo[d]thiazol-2-yl)phenol (HL6): This ligand was purchased
from Sigma–Aldrich and used without further purification.
[Pt(phos)(py-1,2,4-triaz-tol)] (4): PtII precursor P1 (0.100 g,
0.057 mmol) and HL4 (0.027 g, 0.114 mmol) were used for this re-
action A yellowish solid (72 mg, 58%) was obtained. 1H NMR
(300 MHz, CD2Cl2): d=9.38 (t, J=2.0 Hz, 1H), 8.91 (d, J=5.6 Hz,
1H), 8.20 (t, J=7.8 Hz, 3H), 8.01 (td, J=7.8, 1.5 Hz, 1H), 7.68 (dd,
J=8.6, 1.9 Hz, 2H), 7.41 (dd, J=2.4, 1.5 Hz, 2H), 7.29 (d, J=7.9 Hz,
2H), 7.27–7.21 (m, 1H), 7.17 (t, J=2.2 Hz, 1H), 7.02 (dd, J=8.6,
2.5 Hz, 2H), 1.56 (s, 18H), 1.53 (s, 10H), 1.27 (s, 5H), 1.21 (s, 20H),
1.13 (s, 10H), 1.01–0.76 ppm (m, 5H); MS (ESI+, MeOH/CHCl3): m/z
calcd for C56H74N4O3PPt: 1076.51412 [M+H]+; found: 1076.51437.
[{Pt-(m-Cl){k2-P,C-P(OC6H2-2,4-tBu2)(OC6H3-2,4-tBu2)2}}2]
(P1):
Tris(2,4-di-tert-butylphenyl) phosphite (934 mg, 1.44 mmol) and po-
tassium tetrachloroplatinate (600 mg, 1.44 mmol) were combined
in 2-methoxyethanol (48 mL) and heated to 1408C under nitrogen
overnight. The clear solution was cooled to room temperature and
the solvent was removed under reduced pressure. The off-white
residue was dissolved in dichloromethane and filtered through
a pad of celite. The filtered solution was then concentrated under
reduced pressure and the product was precipitated from dichloro-
methane with ethanol to yield a white solid. The supernatant was
removed and the solid dried under vacuum (1.27 g 50%).[11,40]
[Pt(phos)(phenoxy-benzoxazole)] (5): PtII precursor P1 (0.5 g,
0.29 mmol) and HL5 (0.12 g, 0.57 mmol) were used for this reaction
A white solid (80 mg, 13%) was obtained. 1H NMR (300 MHz,
CD2Cl2): d=8.39–8.31 (m, 1H), 8.28 (t, J=2.5 Hz, 1H), 7.96 (dt, J=
8.1, 2.0 Hz, 3H), 7.63–7.54 (m, 1H), 7.48–7.40 (m, 1H), 7.40–7.25 (m,
4H), 7.17 (dd, J=8.6, 0.9 Hz, 1H), 7.10 (t, J=2.4 Hz, 1H), 6.95 (dd,
J=8.6, 2.5 Hz, 2H), 6.73 (ddd, J=8.1, 6.9, 1.1 Hz, 1H), 1.45 (s, 9H),
1.43 (s, 18H), 1.20 (s, 18H), 1.05 ppm (s, 9H); MS (ESI+, MeOH): m/z
calcd for C55H71NO5PPt: 1051.4717 [M+H]+; found: 1051.4664; m/z
calcd for C55H70NNaO5PPt: 1073.4536 [M+Na]+: found: 1073.4499;
elemental analysis calcd (%) for C55H70NO5PPt: C 62.84, H 6.71, N
1.33; found: C 62.7, H 6.71, N 1.21.
General synthetic route for the preparation of the complexes 1–
6:
[{Pt-(m-Cl){k2-P,C-P(OC6H2-2,4-tBu2)(OC6H3-2,4-tBu2)2}}2]
(P1)
(1 equiv) together with the ancillary ligand (2 equiv) were heated
to 508C in a 1:1 mixture of dichloromethane and methanol over-
night. The solvents were removed under reduced pressure and the
crude reaction mixture was purified through column chromatogra-
phy on silica, using a 6:4 mixture of dichloromethane and cyclo-
hexane as eluent. The fractions containing the product were col-
lected, the solvent was removed under reduced pressure, and the
resulting solid was re-crystallized from hexane.
[Pt(phos)(phenoxy-benzothiazole)] (6): PtII precursor P1 (1 g,
0.57 mmol) and HL6 (0.24 g, 1.04 mmol) were used for this reac-
[Pt(phos)(py-pyr-CF3)] (1): PtII precursor P1 (0.1 g, 0.06 mmol) and
HL1 (0.013 g, 0.06 mmol) were used for this reaction. A slightly
1
tion. A
yellow solid (314 mg, 26%) was obtained. 1H NMR
yellow solid (43 mg, 81%) was obtained. H NMR (300 MHz, CDCl3):
(400 MHz, CD2Cl2): d=8.42 (dt, J=7.1, 3.1 Hz, 1H), 8.15–7.95 (m,
1H), 7.83–7.77 (m, 1H), 7.48 (dd, J=8.5, 1.9 Hz, 2H), 7.42–7.33 (m,
2H), 7.33–7.19 (m, 5H), 7.07 (t, J=2.3 Hz, 1H), 7.04 (d, J=8.1 Hz,
1H), 6.78 (dd, J=8.5, 2.5 Hz, 2H), 6.62–6.55 (m, 1H), 1.44 (s, 9H),
1.23 (s, 36H), 1.01 ppm (s, 9H); MS (ESI+, MeOH): m/z calcd for
C55H71NO4PPtS: 1067.4488 [M+H]+; found: 1067.4472; m/z calcd
for C55H70NNaO4PPtS: 1089.4308 [M+Na]+; found: 1089.4301; ele-
mental analysis calcd (%) for C55H70NO4PPtS: C 61.90, H 6.61, N
1.31; found: C 62.47, H 6.73, N 1.19.
d=9.41–9.14 (m, 1H), 8.87 (d, J=5.5 Hz, 1H), 7.83 (td, J=7.8,
1.4 Hz, 1H), 7.73–7.57 (m, 3H), 7.36–7.31 (m, 2H), 7.09 (t, J=2.2 Hz,
1H), 7.02 (ddd, J=5.6, 4.7, 1.3 Hz, 1H), 6.99–6.90 (m, 2H), 6.87 (d,
J=9.7 Hz, 1H), 1.52 (s, 18H), 1.44 (s, 9H), 1.19 (s, 18H), 1.07 ppm
(s, 9H); MS (ESI+, MeOH/CHCl3): m/z calcd for C51H67F3N3O3PPt:
1053.46165 [M+H]+; found: 1053.46165; m/z calcd for
C51H66F3N3O3PPtNa: 1075.44306 [M+Na]+; found: 1075.44930.
[Pt(phos)(py-pyr-ada)] (2): PtII precursor P1 (0.754 g, 0.43 mmol)
and HL2 (0.24 g, 0.86 mmol) were used for this reaction. An off-
white solid (450 mg, 68%) was obtained. 1H NMR (400 MHz,
CD2Cl2): d=9.56–9.32 (m, 1H), 8.83 (d, J=5.6 Hz, 1H), 7.79 (td, J=
8.0, 1.5 Hz, 1H), 7.68 (dd, J=8.6, 1.8 Hz, 2H), 7.61 (d, J=7.7 Hz,
1H), 7.38 (dt, J=17.7, 8.9 Hz, 2H), 7.11 (t, J=2.2 Hz, 1H), 7.02 (dd,
J=8.6, 2.5 Hz, 2H), 6.96 (ddd, J=7.3, 5.7, 1.3 Hz, 1H), 6.49 (d, J=
1.5 Hz, 1H), 2.13 (d, J=2.5 Hz, 6H), 2.09 (s, 3H), 1.83 (t, J=2.8 Hz,
6H), 1.55 (s, 18H), 1.48 (s, 9H), 1.21 (s, 18H), 1.10 ppm (d, J=
7.8 Hz, 9H); MS (ESI+, MeOH): m/z calcd for C60H83N3O3PPt:
1119.5819 [M+H]+; found: 1119.5801; m/z calcd for
C60H82N3NaO3PPt: 1141.5638 [M+Na]+; found: 1141.5602; elemental
analysis calcd (%) for C46H61N3O2PPt: C 64.38, H 7.38, N 3.75; found:
C 64.57, H 7.55, N 3.57.
X-ray diffraction
Data sets were collected with a Nonius Kappa CCD diffractometer.
Programs used: data collection, COLLECT;[41] data reduction,
Denzo-SMN;[42] absorption correction, Denzo;[43] structure solution,
SHELXS-97;[44] structure refinement, SHELXL-97;[45] and graphics,
XP.[46]
X-ray crystal structure analysis of complex 6: Formula
C55H70NO4PPtS; M=1067.24; yellow crystal; 0.33ꢂ0.13ꢂ0.10 mm3;
a=10.7222(1), b=19.0007(3), c=25.4732(4) ꢁ; b=101.569(1)8; V=
5084.20(12) ꢁ3; 1calcd =1.394 gcmꢀ3; m=2.877 mmꢀ1; empirical ab-
sorption correction (0.450ꢃTꢃ0.761); Z=4; monoclinic; space
group P21/c (No. 14); l=0.71073 ꢁ; T=223(2) K; w and f scans;
[Pt(phos)(py-1,2,4-triaz-ada)] (3): PtII precursor P1 and HL3 were
used for this reaction. Column chromatography was performed
with dichloromethane/methanol (97:3) as eluent. An off-white solid
26796 reflections collected (ꢄh, ꢄk, ꢄl); [(sinq)/l]=0.60 ꢁꢀ1
;
1
(0.73 g, 81.3%) was obtained. H NMR (300 MHz, CD2Cl2): d=9.42–
8374 independent (Rint =0.052) and 7708 observed reflections [I>
2s(I)]; 586 refined parameters; R=0.073; wR2 =0.211; max. (min.)
9.16 (m, 1H), 8.86 (d, J=5.7 Hz, 1H), 8.06 (d, J=7.6 Hz, 1H), 7.95
Chem. Eur. J. 2015, 21, 1 – 13
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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