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Compound 2a: In a 50 mL Schlenk round-bottom flask, 0.360 g
(15 mmol, 1.5 equiv) sodium hydride is suspended in 5 mL of dry
DMSO. The mixture was cooled using an ice bath while 1.031 g
(10 mmol) benzonitrile and 1.118 g (12 mmol, 1.2 equiv) aniline are
added via syringe. The reaction was stirred for one hour at this
temperature and then allowed to warm to room temperature
while stirring overnight. Deionized water was slowly added while
the mixture is again cooled in an ice bath and the precipitate col-
lected and washed with an excess of deionized water. After drying
in vacuo, the solid was triturated with isohexanes and again dried
under reduced pressure (1.42 g, 72%). M.p. 1038C. 1H NMR in
CDCl3 (300 MHz) d 7.84 (d, J=6.7 Hz, 2H, CHarom), 7.55–7.40 (m, 3H,
CHarom), 7.40–7.30 (m, 2H, CHarom), 7.14–6.94 (m, 3H, CHarom), 4.94
(brs, 2H, NH2). 13C NMR in CDCl3 (75 MHz) d 130.9 (CHarom), 129.7
(CHarom), 128.8 (CHarom), 127.1 (CHarom), 123.5 (CHarom), 122.0 (CHarom).
Anal. calcd for C13H12N2: C 79.56%; H 6.16%; N 14.27%. Found: C
79.57%; H 6.39%; N 14.17%.
room temperature, 0.641 g (6.4 mmol, 4 equiv) acetylacetone and
0.885 g (6.4 mmol, 4 equiv) potassium carbonate are added and
stirred at room temperature for 21 hours and afterwards at 1008C
for six hours. All volatiles are removed in vacuo and the residue is
washed with ca. 40 mL of distilled water. The remaining solid is fil-
tered, dried at 608C overnight and extracted with DCM. The prod-
uct is purified by flash column chromatography with a gradient of
isohexanes/ethyl acetate (2:1) to pure ethyl acetate. The com-
pound is dissolved in DCM and run over a plug of Celite. After re-
moval of all volatiles under reduced pressure, the analytically pure
product is obtained after washing the solid with isohexanes and
diethyl ether (3ꢂ5 mL each) and drying in vacuo. (155 mg, 18%).
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M.p. 2538C. H NMR in CDCl3 (300 MHz) d 7.82 (dd, J=7.5, 1.4 Hz,
1H, PtCCH of N3-Ph), 7.74–7.57 (m, 3H, CHpara/meta of C2-Ph), 7.46
(dd, J=10.9, 9.3 Hz, 2H, CHortho of C2-Ph), 7.00–6.80 (m, 2H, CHpara
of N3-Ph & NCH), 6.63 (t, J=7.2 Hz, 1H, CHmeta of N3-Ph), 6.18 (d,
J=8.0 Hz, 1H, CHortho of N3-Ph), 5.43 (s, 1H, COCH), 3.47 (s, 3H,
NCH3), 2.00 (s, 3H, COCH3), 1.95 (s, 3H, COCH3). 13C-NMR in CDCl3
(75 MHz) d 184.9 (CO), 184.7 (CO), 148.1 (Ci of N3-Ph), 139.5 (NCN),
133.0 (PtCCH of N3-Ph), 132.1 (PtCN), 131.9 (CHpara of C2-Ph), 130.5
(CHortho of C2-Ph), 129.9 (CHmeta of C2-Ph), 129.5 (PtCCH), 125.5
(CHpara of N3-Ph), 124.5 (Ci of C2-Ph), 122.4 (CHmeta of N3-Ph), 120.2
(NCH), 112.9 (CHortho of N3-Ph), 102.0 (COCH), 34.3 (NCH3), 28.2
(COCH3), 28.1 (COCH3). 195Pt NMR in CDCl3 (64 MHz) dꢀ3369.4 (s).
MS (ESI) m/z=528.3 [M+H]+, 955.5 [2M-acac]+. Anal. calcd for
Compound 3a: In a 100 mL round-bottom flask, 2.944 g (15 mmol)
of compound 2a and 4.710 g (30 mmol, 2 equiv) of a chloroacetal-
dehyde in water (c=50%) are dissolved in 40 mL chloroform. The
mixture is refluxed for 24 hours and subsequently quenched with a
saturated sodium bicarbonate solution in water. The aqueous
phase is extracted with dichloromethane. After drying the organic
phase over magnesium sulfate, the product is isolated by column
chromatography with the eluent ethyl acetate (2.21 g 68%). M.p.
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C
C21H20N2O2Pt 0.16 CH2Cl2: C 46.97%; H 3.79%; N 5.18%; Found: C
738C. H NMR in CDCl3 (300 MHz) d 7.44–7.37 (m, 5H, CHarom), 7.30–
7.21 (m, 6H, CHarom), 7.17 (d, J=1.3 Hz, 1H, CHarom). 13C NMR in
CDCl3 (75 MHz) d 146.7 (Ci), 138.5 (Ci), 130.1 (Ci), 129.6 (CHarom),
128.8 (CHarom), 128.7 (CHarom), 128.6 (CHarom), 128.3 (2 CHarom), 126.0
(CHarom), 123.0 (CHarom). Anal. calcd for C15H12N2: C 81.79%; H 5.49%;
N 12.72%. Found: C 81.75%; H 5.62%; N 12.46%.
47.25%; H 3.48%; N 5.29%.
Compound 7aa: In a flame dried Schlenk tube, 0.615 g (1.6 mmol)
of compound 5a and 0.185 g (0.8 mmol, 0.5 equiv) silver(I) oxide
are dissolved in 40 mL dry DMF and heated to 758C for 23 h. After
adding 0.599 g (1.6 mmol, 1 equiv) Pt(COD)Cl2, the mixture is
stirred at room temperature for three hours and subsequently
heated to 1308C for another 21 hours. The solution is cooled to
room temperature, 0.320 g (3.2 mmol, 2 equiv) acetylacetone and
0.442 g (3.2 mmol, 2 equiv) potassium carbonate are added and
stirred at room temperature for 21 hours and afterwards at 1008C
for six hours. All volatiles are removed in vacuo and the residue is
washed with ca. 40 mL of distilled water. The remaining solid is fil-
tered, dried at 608C overnight and extracted with DCM. The prod-
uct is purified by flash column chromatography with a gradient of
isohexanes/ethyl acetate (3:1) to isohexanes/ethyl acetate (2:1).
After removal of all volatiles under reduced pressure, the analyti-
cally pure product is obtained after washing the solid with isohex-
anes and diethyl ether (3ꢂ5 mL each) and drying in vacuo.
Compound 4a: In a sealed tube, 1.101 g (5 mmol) of compound
3a and 1.434 g (10 mmol, 2 equiv) methyl iodide are dissolved in
3 mL THF. The mixture is heated to 1108C for 24 hours. The precipi-
tate is collected, washed with small volumes of THF and diethyl
ether and subsequently dried in vacuo (1.50 g, 83%). M.p. 2438C.
1H NMR in [D6]DMSO (300 MHz) d 8.18 (d, J=2.1 Hz, 1H, CHarom),
8.12 (d, J=2.1 Hz, 1H, CHarom), 7.64–7.56 (m, 3H, CHarom), 7.56–7.51
(m, 2H, CHarom), 7.51–7.46 (m, 3H, CHarom), 7.44–7.38 (m, 2H, CHarom),
3.79 (s, 3H, NCH3). 13C-NMR in [D6]DMSO (75 MHz) d 144.3 (Ci),
135.1 (Ci), 132.0 (CHarom), 130.9 (CHarom), 130.1 (CHarom), 129.7
(CHarom), 129.0 (CHarom), 126.2 (CHarom), 123.7 (CHarom), 123.5 (CHarom),
121.4 (Ci), 35.9 (NCH3). Anal. calcd for C16H15IN2: C 53.06%; H
4.17%; N 7.73%. Found: C 52.83%; H 3.81%; N 7.75%.
Compound 5a: In a Schlenk tube, 1.652 g (7.5 mmol) of compound
3a, 3.311 g (9 mmol, 1.2 equiv) diphenyliodonium tetrafluoroborate
and 0.075 g (0.38 mmol, 0.05 equiv) copper(ii) acetate monohy-
drate are dissolved in 20 mL DMF. The mixture is heated to 1008C
for 18 hours. All volatiles are removed under reduced pressure and
the product is crystallized from hot methanol. The precipitate is
collected and washed with diethyl ether and dried in vacuo
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(463 mg, 49%). M.p. 3008C. H NMR in CDCl3 (600 MHz) d 7.87 (dd,
J=7.6, 1.5 Hz, 1H, PtCCH of N3-Ph), 7.56–7.51 (m, 1H, CHpara of C2-
Ph), 7.50–7.43 (m, 2H, CHmeta of C2-Ph), 7.39–7.36 (m, 2H, CHortho of
C2-Ph), 7.36–7.31 (m, 3H, CHpara/meta of N1-Ph), 7.20–7.16 (m, 2H,
CHortho of N1-Ph), 7.11 (s, 1H, NCH), 6.97 (td, J=7.4, 1.2 Hz, 1H,
CHpara of N3-Ph), 6.69–6.64 (m, 1H, CHmeta of N3-Ph), 6.31 (dd, J=
8.1, 1.2 Hz, 1H, CHortho of N3-Ph), 5.44 (s, 1H, COCH), 2.02 (s, 3H,
COCH3), 1.94 (s, 3H, COCH3). 13C-NMR in CDCl3 (151 MHz) d 185.0
(CO), 184.8 (CO), 147.9 (Ci of N3-Ph), 139.4 (NCN), 136.2 (Ci of N1-
Ph), 133.1 (PtCCH of N3-Ph), 132.3 (PtCN), 131.6 (CHpara of C2-Ph),
131.0 (CHortho of C2-Ph), 130.1 (PtCCH of N3-Ph), 129.6 (CHmeta of
C2-Ph), 129.5 (CHmeta of N1-Ph), 129.2 (CHpara of N1-Ph), 126.0
(CHortho of N1-Ph), 125.8 (CHpara of N3-Ph), 124.5 (Ci of C2-Ar), 122.5
(CHmeta of N3-Ph), 120.9 (NCH), 113.6 (CHortho of N3-Ph), 102.0
(COCH), 28.2 (COCH3), 28.0 (COCH3). 195Pt NMR in CDCl3 (64 MHz)
dꢀ3371.6 (s). MS (ESI) m/z=590.3 [M+H]+, 1079.5 [2m+H]+. Anal.
calcd for C26H22N2O2Pt: C 52.97%; H 3.76%; N 4.75%. Found: C
52.65%; H 3.57%; N 4.75%.
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(2.55 g, 89%). M.p. 2748C. H NMR in [D6]DMSO (300 MHz) d 8.43
(s, 2H, CHarom), 7.62–7.26 (m, 15H, CHarom). 13C-NMR in [D6]DMSO
(75 MHz) d 144.5 (Ci), 135.0 (Ci), 131.8 (CHarom), 131.2 (CHarom), 130.3
(CHarom), 129.7 (CHarom), 128.6 (CHarom), 126.4 (CHarom), 124.0 (CHarom),
121.6 (Ci). Anal. calcd for: C21H17BF4N2: C 65.65%; H 4.46%; N
7.29%. Found: C 65.75%; H 4.74%; N 7.33%.
Compound 6aa: In a flame dried Schlenk tube, 0.580 g (1.6 mmol)
of compound 4a and 0.297 g (1.28 mmol, 0.8 equiv) silver(i) oxide
are dissolved in 40 mL dry DMF and heated to 758C for 23 h. After
adding 599 mg (1.6 mmol, 1 equiv) Pt(COD)Cl2, the mixture is
stirred at room temperature for three hours and subsequently
heated to 1308C for another 21 hours. The solution is cooled to
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Chem. Eur. J. 2018, 24, 1 – 11
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