10.1002/ejic.201801194
European Journal of Inorganic Chemistry
FULL PAPER
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Anal. calcd for C21H41I3MoN3P2: C, 28.9.; H, 4.7; N, 4.8. Found: C, 29.6;
H, 4.3; N, 4.9.
31P NMR (162.0 MHz, CD2Cl2, 300 K): δ = 139.7 (s, 2P, PPh2) ppm.
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IR (ATR): ṽ = 3443 (br, w), 3114 (br, m), 3036 (w), 2961 (m), 2903 (w),
2867 (m), 1614 (sh), 1604 (m), 1586 (sh), 1563 (m), 1451 (s), 1390 (m),
1370 (m), 1302 (w), 1282 (w), 1197 (m), 1173 (m), 1100 (w), 1094 (w),
1044 (m), 1023 (m), 1000 (m), 988 (m), 939 (m), 901 (w), 874 (m), 822 (m),
796 (s), 730 (m), 694 (w), 670 (w), 636 (m), 616 (w), 579 (w), 551 (w), 535
(w), 482 (m), 466 (s), 450 (w), 432 (m), 385 (w) cm-1.
NaxHg reduction of [MoCl3(H-PN3PPh)] (2a) with 2 equivalents PMe2Ph
To sodium amalgam (210 mg, 9.13 mmol Na, 2 mL Hg) and 10 mL THF
were added 200 mg (294 µmol) [MoCl3(H-PN3PPh)] (2a), 81.2 mg
(588 µmol) PMe2Ph and further 10 mL THF. The reaction mixture was
stirred at room temperature for 20 h. The supernatant solution was
separated from NaxHg, concentrated in vacuum and filtered over neutral
Al2O3. The solvent was removed in vacuum and the product was dried for
a short time in vacuum.
IR (ATR): ṽ = 2034 (w), 1962 (s) (N2 stretching vibration) cm-1.
31P NMR (162.0 MHz, THF-d8, 300 K): cis-[Mo(N2)(PMe2Ph)2(H-PN3PPh)]
2
2
(5a): δ = 106.0 (dd, JPP=21.1 Hz, JPP=5.5 Hz, 2P, PPh2), 17.4 (dt,
2JPP=17.1 Hz, JPP=5.5 Hz 1P, PMe2Ph (axial)), 7.5 (td, JPP=21.1 Hz,
2JPP=17.1 Hz, PMe2Ph (equatorial)) ppm. trans-[Mo(N2)2(PMe2Ph)(H-
PN3PPh)] (5b): δ = 107.1 (d, 2JPP=4.4 Hz, 2P, PPh2), 22.3 (t, 2JPP=4.4 Hz,
PMe2Ph) ppm. trans-[Mo(N2)(PMe2Ph)2(H-PN3PPh)] (5c): δ = 98.9 (t,
2JPP=21.1 Hz, 2P, PPh2), 9.8 (t, 2JPP=21.1 Hz, PMe2Ph) ppm.
2
2
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NaxHg reduction of [MoCl3(H-PN3PPh)] (2a) with 1 equivalents PMe2Ph
To sodium amalgam (41 mg, 1.78 mmol Na, 1 mL Hg) and 5 mL THF were
added 200 mg (294 µmol) [MoCl3(H-PN3PPh)] (2a), 45.0 mg (324 µmol)
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31P NMR (162.0 MHz, THF-d8, 300 K): trans-[Mo(N2)2(PMe2Ph)(H-
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1P, PMe2Ph (axial)), 7.6 (td, JPP=20.9 Hz, JPP=16.6 Hz, PMe2Ph
(equatorial)) ppm. trans-[Mo(N2)(PMe2Ph)2(H-PN3PPh)] (5c): δ = 98.9 (t,
2JPP=21.2 Hz, 2P, PPh2), 9.9 (t, 2JPP=21.2 Hz, PMe2Ph) ppm.
Catalytic reduction of dinitrogen to ammonia under N2
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The catalytic runs were performed after the following procedure. To the
respective complex (0.01 mmol) and the proton source (48 equiv.) 1 mL
toluene is added under dinitrogen atmosphere. Via a syringe pump the
electron source (36 equiv.) in 4 mL toluene is added dropwise during 1
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Keywords: Nitrogen Fixation • Pincer Ligands • N2-to-NH3
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