techniques. Solvents—if not stated otherwise—were rigorously
purified with appropriate drying agents, distilled and stored
over molecular sieves under nitrogen. Chloronaphthalene was
purchased from Acros as a mixture of 90% of 1-chloronaphthalene
and 10% of 2-chloronaphthalene. Phthalonitrile was sublimed
under reduced pressure prior to use. The electronic spectra were
recorded on a Shimadzu UV-1601 PC-spectrophotometer. IR
spectra were recorded on a Bruker IFS 588 spectrometer. APCI
mass spectra were taken on a Finnigan LTQ-FT Spectrometer
using methanol as solvent. MALDI–TOF mass spectra were taken
on a Bruker Biflex III using pyrene as matrix. Elemental analysis
of C, H and N elements was carried out using an Elementar, Vario
EL. 1H-NMR spectra of the phthalocyanines were recorded on a
Bruker AMX 500.
[PcW(NtBu)Cl] 3. 400 mg phthalonitrile (3.13 mmol) and
367 mg [W(NtBu)2Cl2(NH2tBu)] (0.78 mmol). Yield: 35 mg, (6%).
Anal. calcd for C36H25ClN9W: C 53.85, H 3.14, N 15.70, Cl 4.41.
Found: C 51.33, H 4.01, N 15.40, Cl 5.15. UV-vis lmax/nm (1-
chloronaphthalene): 746 (sh), 708 (s), 348 (s). IR nmax(KBr)/cm-1:
2994 (s, n(CHaliph.)), 1604 (w), 1467 (m), 1408 (w), 1332 (s), 1286
(m), 1162 (w), 1115 (s), 966 (s), 956 (w), 891 (m), 853 (w), 773 (m),
750 (m), 724 (s), 571 (w). EPR (1-chloronaphthalene/toluene 1 : 3,
293 K): giso = 1.959. MALDI-TOF-MS (m/z) 802.4 [M+], 767.4
[M+ - Cl]. APCI-HRMS (m/z) 767.1750 [M+ - Cl], C36H25N9W
requires 767.1737.
[PcW(NMes)Cl] 4. 520 mg phthalonitrile (4.06 mmol) and
577 mg [W(NMes)2Cl2(dme)] (0.94 mmol). Yield: 580 mg (71%).
Anal. calcd for C41H27ClN9W: C 56.93, H 3.14, N 14.57,
Cl 4.1. Found: C 56.17, H 3.15, N 13.90, Cl 5.01. UV-vis
[Mo(NtBu)2Cl2(dme)]18 [Mo(NMes)2Cl2(dme)],19 [W(NtBu)2-
Cl2(H2NtBu)],20 [W(NMes)2Cl2(dme)],19 [W(NTs)2Cl2],21 [Re(Nt-
Bu)2Cl3]29 and [Re(NMes)2Cl3py]29 were prepared according to
literature procedures.
l
max/nm (1-chloronaphthalene): 870.0 (m), 731.0 (s), 664.0 (m).
IR nmax(KBr)/cm-1: 1605 (w), 1468 (m), 1404 (w), 1329 (s), 1284
(m), 1161 (w), 1117 (s), 966 (s), 951 (w), 893 (m), 853 (w), 773 (m),
749 (m), 724 (s), 571 (w). EPR (1-chloronaphthalene/toluene 1 : 3,
130 K): g1 = 1.927, g2 = 1.908, g3 = 1.911. MALDI-TOF-MS (m/z)
864.4 [M+], 829.4 [M+ - Cl]. APCI-HRMS (m/z) 829.1902 [M+ -
Cl], C41H27N9W requires 829.1983.
General Procedure for the Preparation of 1–7
A
mixture of 4.4 equiv. phthalonitrile and 1 equiv. of
the respective bis(imido) precursor (1: [Mo(NtBu)2Cl2(dme)],
2: [Mo(NMes)2Cl2(dme)], 3: [W(NtBu)2Cl2(NH2NtBu)], 4:
[W(NMes)2Cl2(dme)], 5: [W(NTs)2Cl2], 6: [Re(NtBu)2Cl3], 7:
[Re(NMes)2Cl3py]) was finely ground in a mortar under nitrogen
until a homogeneous powder was obtained. The mixture was
quickly heated at melt at 210 ◦C for 20 min by using a preheated
metal bath of Wood alloy. The produced dark-green solid was
suspended in 50 mL of toluene and the suspension was treated
with ultrasound at 70 ◦C for 2 h. The precipitate was collected on
a glass frit and purified by successive extractions with refluxing
toluene (10 ¥ 50 mL), MeCN (10 ¥ 50 mL) and finally washed
with pentane. The black-green solid was dried at 140 ◦C and 10-5
mbar for 5 h.
[PcW(NTs)Cl] 5. 200 mg phthalonitrile (1.56 mmol) and
136 mg [W(NTs)2Cl2] (0.35 mmol). Yield: 137 mg (45%). Anal.
calcd for C39H23ClN9O2SW: C 51.99, H 2.57, N 13.99. Found: C
51.26, H 2.91, N 13.33. UV-vis lmax/nm (1-chloronaphthalene):
762 (s), 385 (s). IR nmax(KBr)/cm-1: 2915 (w), 1619 (m), 1601 (w),
1519 (w), 1464 (s), 1326 (s), 1287 (s), 1154 (m), 1117 (m), 1057 (s),
892 (w), 768 (m), 725 (s), 552 (m). EPR (solid state, 8 K): g1 = 1.88.
APCI-HRMS (m/z) 865.1207 [M+ - Cl], C39H23N9O2SW requires
865.1203.
[PcRe(NtBu)Cl] 6. 400 mg phthalonitrile (3.12 mmol) and
308 mg [Re(NtBu)2Cl3] (0.71 mmol). Yield: 260 mg (42%). Anal.
calcd for C36H25N9ClRe: C 53.69, H 3.13, N 15.65, Cl 4.4. Found:
C 51.84, H 2.70, N 17.25, Cl 4.7. (Despite the diligent purification
of the product and multiple attempts, no better elemental analysis
could be obtained). UV-vis lmax/nm (1-chloronaphthalene): 820
(sh), 700 (s), 341.0 (w), 323.0 (s). IR nmax(KBr)/cm-1: 2969 (w),
1771 (w), 1717 (w), 1652 (w), 1609 (w), 1558 (w), 1522 (w), 1473
(s), 1409 (w), 1361 (w), 1334 (s), 1287 (m), 1260 (Re N–C), 1184
(w), 1167 (w), 1119 (m), 1101 (m), 1064 (w), 902 (w), 776 (w), 755
(w), 732 (s). 1H-NMR (500 MHz, C6D5Br, 373 K) d (ppm): -1.55
(s, 9 H, CMe3), 8.34–8.47 (m, 8 H, 2,3-Pc), 9.81–9.86 (m, 8 H, 1,4-
Pc). APCI-MS (m/z) 804 [M+], 769 [M+ - C1], MALDI-TOF-MS
(m/z) 805.5 [M+], 770.3 [M+ - Cl].
[PcMo(NtBu)Cl] 1. 282 mg phthalonitrile (22 mmol) and
200 mg [Mo(NtBu)2Cl2(dme)] (5 mmol). Yield: 220 mg (67%).
Anal. calcd for C36H25ClMoN9: C 60.47, H 3.52, N 17.63. Found:
C 59.61, H 4.33, N 17.12. UV-vis lmax/nm (1-chloronaphthalene):
718 (s), 648 (sh), 358 (s). nmax(KBr)/cm-1: 1602 (m), 1463 (m),
1328 (s), 1284 (w), 1265 (m) 1161 (w), 1115 (s), 1063 (m), 973
(w), 893 (m), 802 (w), 772 (w), 750 (m), 728 (s), 570 (w). EPR
(1-chloronaphthalene/toluene 1 : 3, 130 K): g1 = 1.989, g2 = 1.987,
g3 = 1.977. MALDI-TOF-MS (m/z) 716.2 [M+], 681.3 [M+ - Cl],
APCI-HRMS (m/z) 681.1289 [M+ - Cl], C36H25N9Mo requires
681.1282.
[PcMo(NMes)Cl] 2. 282 mg phthalonitrile (22 mmol) and
262 mg [Mo(NMes)2Cl2(dme)] (5 mmol). Yield: 280 mg (72%).
Anal. calcd for C36H25ClMoN9: C 63.36, H 3.50, N 16.22, Cl 4.6.
Found: C 63.84, H 3.76, N 14.55, Cl 5.8. UV-vis lmax/nm (1-
chloronaphthalene): 732 (s), 668 (sh), 364 (s). IR nmax(KBr)/cm-1:
1602 (m), 1462 (m), 1327 (s), 1286 (w), 1260(Mo N–C), 1161 (w),
1114 (s), 1063 (w), 972 (m), 891 (m), 802 (w), 772 (w), 749 (m),
727 (s), 569 (w). EPR (1-chloronaphthalene/toluene 1 : 3, 130 K):
g1 = 1.986, g2 = 1.981, g3 = 1.974. MALDI-TOF-MS (m/z) 778
[M+], 743 [M+ - Cl]. APCI-HRMS (m/z) 743.1439 [M+ - Cl],
C41H27N9Mo requires 743.1438.
[PcRe(NMes)Cl] 7. 898 mg phthalonitrile (7.02 mmol) and
1.02 g [Re(NMes)2Cl3py] (1.60 mmol). Yield: 1.15 g, (83%). Anal.
calcd for C41H27N9ClRe C 56.77, H 3.14, N 14.53, Cl 4.08. Found:
C 52.17, H 2.39, N 15.24, Cl 3.80 (Despite the diligent purification
of the product and multiple attempts, no better elemental analysis
could be obtained). UV-vis lmax(1-chloronaphthalene)/nm 736 (s),
664 (sh), 364 (s), 321.4 (s); IR nmax(KBr)/cm-1 1607 (w), 1474 (m),
1410 (w), 1331 (s), 1287 (w), 1261 (Re N–C) 1167 (m), 1119 (m),
1100 (w), 1063 (w), 901 (m), 872 (w), 807 (w), 775 (m), 754 (m),
727 (s); 1H-NMR (500 MHz, C6D5Br, 373 K) d (ppm) -0.51 (s, 6
H, oMe), 1.12 (s, 3 H, pMe), 5.56 (s, 2 H, Mes), 8.26–8.45 (m, 8 H,
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 1183–1188 | 1187
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