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(d, JPC = 11.9 Hz, C-5), 140.03 (d, JPC = 9.8 Hz, C-4), 127.90 (d,
120 °C. 1H NMR (400 MHz, CDCl3, 20 °C): δ = 8.82 (m, AA′BB′ spin
1JPC = 84.3 Hz, C-3), 124.0 (d, JPC = 9.6 Hz, C-2) ppm. 31P NMR
system, 6 H, 2-H and 6-H), 7.57 (m, 6 H, 3-H and 5-H) ppm. 13C NMR
2
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(162 MHz, CDCl3, 20 °C): δ = 33.2 (s, JPC = 83.9 Hz) ppm. IR (KBr):
(101 MHz, CDCl3, 20 °C): δ = 150.63 (d, JPC = 9.8 Hz, C-2 and C-6),
ν = 656 (m) (P=S) cm–1. HRMS (APCI+): calcd. for [C15H13N3PS]+:
139.91 (d, JPC = 80.3 Hz, C-4), 125.38 (d, JPC = 8.4 Hz, C-3 and C-
1
3
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298.05623; found: 298.05600.
5) ppm. 31P NMR (162 MHz, CDCl3, 20 °C): δ = 38.4 (s) ppm. IR
(KBr): ν = 640 (s) (P=S) cm–1. HRMS (APCI+): calcd. for [C15H13N3PS]+:
˜
Tri(3-pyridyl)phosphine Selenide (3): Crude tri(3-pyridyl)phos-
phane (1), prepared from excess 3-lithiopyridine and PCl3 (7 mmol),
was heated at reflux with Se (6 g, 76 mmol) in toluene (70 mL)
under an argon atmosphere. After evaporation of the solvent, the
residue was extracted with CH2Cl2 (2 × 100 mL). The solvent was
removed from the clear extract and the remaining product was
washed with cold acetone and Et2O to give a pale-yellow solid,
yield 1.96 g (34 %), m.p. 203–205 °C. 1H NMR (400 MHz, CDCl3,
298.05623; found: 298.05596.
Tri(4-pyridyl)phosphine Selenide (7): Crude 4, obtained as de-
scribed above from PCl3 (1.6 mmol), was heated at reflux with Se
powder (0.25 g, 3.2 mmol) in toluene (50 mL) in an inert atmos-
phere for 8 h. After evaporation of the solvent, the residue was
extracted with CH2Cl2. After removal of dichloromethane from the
clear extract, the remaining product was washed with cold acetone
and Et2O to give a colorless solid, yield 0.21 g (38 %), m.p. 240 °C
(dec.). 1H NMR (400 MHz, CDCl3, 20 °C): δ = 8.79 (m, AA′BB′ spin
system, 6 H, 2-H and 6-H), 7.56 (m, 6 H, 3-H and 5-H) ppm. 13C NMR
3
3
20 °C): δ = 8.77 (m, 6 H, 5-H, 6-H), 8.19 (ddt, JPH = 14.2, JHH = 8.0,
4JHH = 2.0 Hz, 3 H, 4-H), 7.47 (ddd, JPH = 7.7, JPH = 4.8, JHH
=
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4
4
2.3 Hz, 3 H, 2-H) ppm. 13C NMR (101 MHz, CDCl3, 20 °C): δ = 153.07
4
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(d, JPC = 2.5 Hz, C-6), 152.31 (d, JPC = 11.5 Hz, C-5), 140.62 (d,
(101 MHz, CDCl3, 20 °C): δ = 150.59 (d, JPC = 9.8 Hz, C-2 and C-6),
2JPC = 10.4 Hz, C-4), 126.66 (d, 1JPC = 75.2 Hz, C-3), 123.99 (d, JPC
=
2
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138.73 (d, JPC = 71.2 Hz, C-4), 125.89 (d, JPC = 8.6 Hz, C-3 and C-
9.7 Hz, C-2) ppm. 31P NMR (162 MHz, CDCl3, 20 °C): δ = 23.7 (s,
5) ppm. 31P NMR (162 MHz, CDCl3, 20 °C): δ = 31.4 (s, JPC = 70.4,
1
1JPC = 75.9, 1JPSe = 770.1 Hz) ppm. 77Se NMR (76 MHz, CDCl3, 20 °C):
1JPSe = 784.7 Hz) ppm. 77Se NMR (76 MHz, CDCl3, 20 °C): δ = –304.7
1
(d, JPSe = 785.9 Hz) ppm. IR (KBr): ν = 575 (m) (P=Se) cm–1. HRMS
1
δ = –275.5 (d, JPSe = 770.1 Hz) ppm. IR (KBr): ν = 574 (m) (P=Se)
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cm–1. HRMS (APCI+): calcd. for [C15H13N3PSe]+: 346.00068; found:
346.00027.
(APCI+): calcd. for [C15H13N3PSe]+: 346.00086; found: 346.00054.
General Procedure for the Preparation of (ZnTPP)3(R3PE) (R = 3-
Py, 4-Py; E = S, Se) Complexes (8–11): The corresponding tripyr-
idylphosphine chalcogenides were stirred in 1:3 molar ratio with
ZnTPP in CH2Cl2 for 30 min. Evaporation of the solvent in vacuo
yielded quantitatively the corresponding complexes as deep-purple
solids, which decompose without melting.
Tri(4-pyridyl)phosphane (4): A solution of iPrMgCl·LiCl in THF
(3.84 mL, 1.27
M) was added dropwise to a stirred solution of 4-
iodopyridine (1 g, 4.88 mmol) in anhydrous Et2O (50 mL) at –60 °C.
After stirring for 90 min at this temperature, a solution of PCl3
(0.22 g, 1.6 mmol) in anhydrous Et2O (20 mL) was slowly added
to the reaction mixture. Stirring was continued overnight and the
temperature was allowed to reach room temperature. The reaction
mixture was poured into degassed water and the phases were sepa-
rated. The aqueous phase was extracted with CH2Cl2 and the com-
bined organic phases were dried with Na2SO4. After evaporation of
the solvents, the crude brown oil afforded colorless X-ray quality
crystals upon standing at room temperature for a few days. The
NMR spectra were identical to those reported.[7] Yield 0.19 g (45 %).
(ZnTPP)3[(3-Py)3PS] (8): From 2 (20.0 mg, 0.07 mmol) and ZnTPP
(136.8 mg, 0.21 mmol), in CH2Cl2 (25 mL). 1H NMR (600 MHz, CDCl3,
3
20 °C): δ = 8.71 (s, 24 H, 7-H), 7.95 (d, JHH = 7.4 Hz, 24 H, 11-H),
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7.74 (t, JHH = 7.5 Hz, 12 H, 13-H), 7.56 (t, JHH = 7.6 Hz, 24 H, 12-
H), 5.51 (br. s, 3 H, 2-H), 4.95 (br. s, 3 H, 4-H), 3.39 (br. s, 3 H, 6-H),
2.65 (br. s, 3 H, 5-H) ppm. 13C NMR (151 MHz, CDCl3, 20 °C): δ =
149.83 (s, C-8), 146.74 (s, C-6) 146.33 (d, 3JPC = 14.3 Hz, C-5), 142.92
(s, C-10), 137.02 (d, 2JPC = 7.8 Hz, C-4), 134.52 (s, C-11), 131.70 (s, C-
Tri(4-pyridyl)phosphine Oxide (5): A solution of 4 (0.15 g,
0.56 mmol) in CH2Cl2 (20 mL) was treated with H2O2 (6 mL, 3 %) and
stirred for 3 h. The aqueous layer was discarded and evaporation of
the solvent from the organic phase yielded the title compound as
a colorless solid, yield 0.15 g (95 %), m.p. 117 °C (dec.). 1H NMR
(400 MHz, CDCl3, 20 °C): δ = 8.84 (m, AA′BB′ spin system, 6 H, 2-H
and 6-H), 7.53 (m, 6 H, 3-H and 5-H) ppm. 13C NMR (101 MHz, CDCl3,
1
7), 127.27 (s, C-13), 126.33 (s, C-12), 124.78 (d, JPC = 85.6 Hz, C-3),
122.04 (d, 2JPC = 9.4 Hz, C-2), 120.63 (s, C-9) ppm. 31P NMR (243 MHz,
CDCl3, 20 °C): δ = 27.4 (s) ppm. IR (KBr): ν = 661 (m) (P=S) cm–1
.
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(ZnTPP)3[(3-Py)3PSe] (9): From 3 (25.0 mg, 0.07 mmol) and ZnTPP
(147.8 mg, 0.21 mmol), in CH2Cl2 (25 mL). 1H NMR (600 MHz, CDCl3,
3
20 °C): δ = 8.70 (s, 24 H, 7-H), 7.94 (d, JHH = 7.2 Hz, 24 H, 11-H),
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7.70 (t, JHH = 7.6 Hz, 12 H, 13-H), 7.53 (t, JHH = 7.5 Hz, 24 H, 12-
H), 5.59 (br. s, 3 H, 2-H), 5.07 (br. s, 3 H, 4-H), 3.73 (br. s, 3 H, 6-H),
3.16 (br. s, 3 H, 5-H) ppm. 13C NMR (151 MHz, CDCl3, 20 °C): δ =
20 °C): δ = 150.65 (d, JPC = 9.9 Hz, C-2 and C-6), 138.92 (d, JPC
=
100.1 Hz, C-4), 125.38 (d, JPC = 8.1 Hz, C-3 and C-5) ppm. 31P NMR
3
(162 MHz, CDCl3, 20 °C): δ = 22.4 (s) ppm. IR (KBr): ν = 1262 (s),
˜
149.96 (s, C-8), 147.36 (m, C-5, C-6), 143.04 (s, C-10), 137.65 (d, 2JPC
=
1017 (s) (P=O) cm–1. HRMS (APCI+): calcd. for [C15H13N3PO]+:
282.07908; found: 282.07902.
8.6 Hz, C-4), 134.63 (s, C-11), 131.82 (s, C-7), 127.37 (s, C-13), 126.42
1
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(s, C-12), 123.96 (d, JPC = 75.9 Hz, C-3), 122.18 (d, JPC = 9.3 Hz, C-
Tri(4-pyridyl)phosphine Sulfide (6): A solution of iPrMgCl·LiCl in
THF (3.84 mL, 1.27 M) was added dropwise to a stirred solution of
2) 120.76 (s C-9) ppm. 31P NMR (243 MHz, CDCl3, 20 °C): δ = 18.9
(s, JPSe = 790.9 Hz) ppm. 77Se NMR (76 MHz, CDCl3, 20 °C): δ =
1
4-iodopyridine (1 g, 4.88 mmol) in anhydrous Et2O (50 mL) at –60 °C.
After stirring for an additional 90 min at this temperature, a solution
of PCl3 (0.22 g, 1.6 mmol) in anhydrous Et2O (20 mL) was slowly
added to the reaction mixture. Stirring was continued overnight
and the temperature was allowed to reach room temperature, after
which the solvent was evaporated in vacuo and dry hot toluene was
added over the remaining solid. The remaining solid was filtered
off with a cannula and the clear solution was heated at reflux with
–253.6 (d, JPSe = 791.0 Hz) ppm. IR (KBr): ν = 574 (m) (P=Se) cm–1
.
1
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HRMS (ESI+, MeOH): calcd. for [C191H125N19PSeZn4]+: 3050.64053;
found: 3050.64759; calcd. for [C147H96N15PSeZn3]+: 2374.48231;
found: 2374.47376; calcd. for [C103H69N11PSeZn2]+: 1698.32177;
found: 1698.32120; calcd. for [C59H41N7PSeZn]+: 1022.16123; found:
1022.16111.
(ZnTPP)3[(4-Py)3PS] (10): From 6 (20.0 mg, 0.07 mmol) and ZnTPP
elemental sulfur (0.1 g, 3.2 mmol) for 8 h. After evaporation of the (136.8 mg, 0.21 mmol), in CH2Cl2 (25 mL). 1H NMR (600 MHz, CDCl3,
solvent, the residue was extracted with Et2O (2 × 50 mL). Upon
cooling to –20 °C, the concentrated extract (ca. 10 mL) gave the
title compound as a colorless solid, yield 0.14 g (30 %), m.p. 118–
3
20 °C): δ = 8.90 (s, 24 H, 7-H), 8.16 (d, JHH = 7.2 Hz, 24 H, 11-H),
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7.79 (t, JHH = 7.5 Hz, 12 H, 13-H), 7.73 (t, JHH = 7.5 Hz, 24 H, 12-
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H), 4.57 (dd, JPH = 13.6, JHH = 5.5 Hz, 6 H, 3-H and 5-H), 2.43 (br.
Eur. J. Inorg. Chem. 2016, 1521–1527
1526 © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim