Aluminum Chloride Mediated Alkynylation of Boron Subphthalocyanine Chloride Using Trimethylsilyl-Capped Acetylenes

Article abstract of DOI:10.1021/acs.joc.5b02719

A mild and versatile procedure is presented for functionalization of boron chloride subphthalocyanine at the axial boron position with trimethylsilyl-protected alkyne nucleophiles in the presence of aluminum chloride. The method allows a large variety of

Full text of DOI:10.1021/acs.joc.5b02719

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Brief Communication
Aluminum Chloride Mediated Alkynylation of Boron
Subphthalocyanine Chloride Using Trimethylsilyl-Capped Acetylenes
Henrik Gotfredsen, Martyn Jevric, Søren Lindbæk Broman, Anne U. Petersen, and Mogens Brøndsted Nielsen
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b02719 • Publication Date (Web): 15 Dec 2015
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Aluminum Chloride Mediated Alkynylation of Boron Subphthalocyanine
Chloride Using Trimethylsilyl-Capped Acetylenes
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Henrik Gotfredsen, Martyn Jevric, Søren L. Broman, Anne U. Petersen, and Mogens Brøndsted Nielsen*
Department of Chemistry, Center for Exploitation of Solar Energy, University of Copenhagen,
Universitetsparken 5, DKꢀ2100 Copenhagen Ø, Denmark
Abstract
A mild and versatile procedure is presented for functionalization of boron-chloride subphthalocyanine at
the axial boron position with trimethylsilyl-protected alkyne nucleophiles in the presence of aluminum
chloride. The method allows a large variety of substituents on the alkyne units, including electron-
donating/withdrawing aryl groups, silyl-protected alkynyl groups, as well as ferrocenyl and azulenyl
groups. In addition, ferrocene itself reacts smoothly under these conditions allowing for directly
anchoring it to the boron of the subphthalocyanine.
Subphthalocyanines (SubPc’s) are redox-active chromophores, which are readily synthesized in a
cyclotrimerization reaction of phthalonitrile in the presence of boron trichloride,1 and they have for these
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reasons found significant interest as molecular entities for organic photovoltaics.2-6 To advance their use,
efficient functionalization methods are pursued,3 for example at the axial boron position. An important
protocol has been developed for substitution of the chloride of the readily achievable boron chloride
SubPc (SubPc-Cl)1 via the triflate intermediate.7 Direct attachment of an acetylide to the boron, forming
a SubPc-C≡C-R compound, is possible via Grignard reactions, which preclude, however, the use of base
sensitive or electrophilic substrates.6, 8-10 The noninvertible nature of the boron center of SubPc is
reminiscent of other systems such as adamantyl bromide11 and perchloroazatriquinacene,12 both of which
have been shown to undergo AlCl3-mediated substitution reactions. Indeed, Morse and Bender13 have
demonstrated the use of AlCl3 in axial functionalization of SubPc-Cl with oxygen, sulfur, and nitrogen
based nucleophiles. Furthermore, Torres and co-workers14 have recently shown that trimethylsilyl (TMS)
capped nucleophiles can be added axially to SubPc-Cl with the expulsion of volatile trimethylsilyl
chloride as the driving force. Rather harsh conditions were, however, necessary (reflux in toluene or
nitrobenzene), and the conditions did not allow trimethylsilylacetylenes as substrates. Inspired by the
work of Bender and Torres, we sought to expand upon the axial reactivity of SubPc-Cl towards
trimethylsilyl-protected terminal alkynes assisted by AlCl3.
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We treated SubPc-Cl with a large selection of TMS-protected alkynes (1a-k) in the presence of AlCl3 in
o-dichlorobenzene (o-DCB) at room temperature, which furnished the SubPc products 2a-k (Scheme 1),
in generally good to high yields as listed in Table 1 (only 2d was isolated in rather low yield), but with
various reaction times needed (until no further change was observed by TLC-inspection, not always
corresponding to complete reaction). Gratifyingly, both electron-poor and electron-rich TMS-protected
arylacetylenes turned to be reactive under these conditions (entries 1-5). In addition, the aryltriflate 1f
(prepared in two steps from 4-bromo-2,6-dimethylphenol, see Experimental Section) was almost
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quantitatively converted to the product 2f (entry 6). We do not attribute the modest yield of the
dimethylaniline product 2d (entry 4) to an inefficient reaction as spot-to-spot conversion was observed by
TLC, but rather to stability issues of the product towards silica gel during chromatographic purification.
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Scheme 1. Axial Functionalization of Boron Subphthalocyanine (for Yields and Details, see Table
1).
Table 1. Yields of Axially Functionalized Subphthalocyanines (see Scheme 1)
Entry
Alkyne substrate
(equiv.)
AlCl3 Reaction Product
Recovered
Alkyne
equiv.
time
(yield)
Substrate
1
2
3
4
5
6
7
8
1a (10)
1b (6)
1c (10)
1d (10)
1e (8)
1f (10)
1g (10)
1h (9)
5
5
5
5
12
5
15 h
16 h
17 h
2 h
3.5 h
18 h
40 h
0.5 h
2a (69%)
2b (89%)
2c (88%)
2d (28%)
2e (86%)
2f (93%)
2g (65%)
2h (97%)
6
6
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1i (10)
1j (9)
1j (0.6)
6
6
3
12
5
2 h
2 h
4 h
5 days
17 h
2i (89%)
2j (57%)
3 (8%)
2k (65%)
4 (76%)
78%
51%
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13
1k (8)
82%
Allyltrimethylsilane (10)
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The procedure was also successful towards alkyne substrates 1g and 1h, furnishing the desired products
2g and 2h in yields of 65 and 97%, respectively (entries 7 and 8). These products are like the iodide 2b
and triflate 2f potential building blocks for further acetylenic scaffolding. We have recently shown that a
terminal alkyne at the axial position, separated by a CH2CH2O spacer to boron, is a convenient handle for
a variety of metal-catalyzed cross-coupling reactions.15
Ferrocene is often used in conjunction with SubPc, targeting systems for which light-induced charge-
separation can be achieved,8, 16-19 and therefore we wanted to explore the procedure’s susceptibility
towards substrates incorporating ferrocene. Using an excess of the readily achievable mono-/di-
ethynylferrocene substrates 1i and 1j,20, 21 SubPc-Cl was converted to the SubPc-Fc conjugates 2i and 2j
(Fc = ferrocenyl) in yields of 78 and 57%, respectively (entries 9 and 10). In the latter case, 4% of the
SubPc-Fc-SubPc triad 3 was isolated as well. Conjugate 2i has previously been prepared in a yield of
26% by Nemykin and coworkers8 via the Grignard reagent of ethynylferrocene and SubPc-Cl, and our
procedure hence presents a significant improvement. In addition, by subjecting the substrate 1j to an
excess of SubPc-Cl (1.8 equiv), the procedure provided direct access to the triad 3, albeit only in 8%
yield (entry 11). The azulene moiety was readily incorporated via the substrate 1k (for its preparation, see
Experimental Section), furnishing the conjugate 2k in a yield of 65% (entry 12). Interestingly, with the
cyano-containing substrates 1e and 1k, a larger excess of AlCl3 was necessary to carry out the desired
substitutions. A possible explanation could be that the AlCl3-reserve is depleted by the CN groups of the
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TMS-nucleophiles. Finally, SubPc-Cl was treated with allyltrimethylsilane and AlCl3, which gave the
product 4 in a yield of 76% (entry 13). Conveniently, when the TMS-protected alkyne is either expensive
or difficult to obtain, the excess can to a large extent be re-isolated (entries 9, 10, and 12). In most cases
8-10 equiv. of the alkyne were employed, but entry 2 shows an example with successful conversion using
only 6 equiv. The structures of 2a, 2j, and 2k were confirmed by X-ray crystallographic analysis (Figure
1) as was the structure of 2i (see SI; structure has been reported previously8). In regard to the optical
properties, the variation in axial substitution had little influence on the characteristic longest-wavelength
SubPc absorption maximum (ca. 566-570 nm in CHCl3; for absorption spectra, see SI).
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Figure 1. Molecular structures (with displacement ellipsoids at 50% probability for non-H atoms) of 2a
(left; crystals grown from CHCl3/heptane; CCDC 1439146), 2j (middle; crystals grown from
EtOAc/heptane; CCDC 1439351), and 2k with co-crystallized heptane molecule (right; crystals grown
from benzene/heptane; CCDC 1439324).
The reaction conditions were also found to facilitate a Friedel-Crafts like reaction between SubPc-Cl and
parent ferrocene to furnish the SubPc-Fc conjugate 5 in a yield of 50% where ferrocene is directly
anchored to boron (Scheme 2), confirmed by X-ray crystallography (see SI). This compound was
previously synthesized via the mono-lithioferrocene and SubPc-Cl in a yield of 21%;8 again, the present
procedure is a significant improvement. Finally, 1,2,3-trimethoxybenzene was subjected to the reaction
conditions, in the hope that this highly activated aromatic substrate would give access to another Friedel-
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Crafts like product. However, rather than reacting via the C-5 position, the central methoxy group had
gone through a demethylation and reacted through the oxygen to form the O-substituted SubPc 6, albeit in
low yield.
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Scheme 2. Reactions with Ferrocene and 1,2,3-Trimethoxybenzene Nucleophiles.
In conclusion, a mild and versatile procedure for the axial functionalization of SubPc-Cl with electron
poor/rich TMS-protected alkynes has been developed, allowing for ready preparation of
subphthalocyanine-ferrocene/azulene conjugates. The protocol is operationally very simple, not requiring
inert conditions. Some of the products, in particularly those containing a silylprotected alkyne unit, are
potential building blocks for further acetylenic scaffolding.
Experimental Section
General Methods. All reagents and solvents were obtained from commercial suppliers and used as
received unless otherwise stated. Boron subphthalocyanine chloride (SubPc-Cl) was prepared according
to a literature procedure.1 Dry THF was obtained by distillation from a Na/benzophenone couple. Dry
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pyridine was obtained from storage over KOH. Purification by column chromatography was carried out
on silica gel (SiO2, 60Å, 40–63 µm). Thin-layer chromatography (TLC) was carried out using
commercially available aluminum sheets pre-coated with silica gel with fluorescence indicator and
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visualised under UV light at 254 or 360 nm. H and 13C NMR spectra were recorded on a 500 MHz
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instrument equipped with a non-inverse cryoprobe. The B NMR spectra were recorded on a 500 MHz
instrument equipped with a broad-band probe. Chemical shift values are quoted in ppm and coupling
constants (J) in Hz. 1H and 13C NMR spectra are referenced against the residual solvent peak (CDCl3 δH =
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7.26 ppm, δC = 77.16 ppm; C6D6 δH = 7.16 ppm, δC = 128.06 ppm). B NMR spectra are referenced
against an external standard of BF3 diethyl etherate (BF3•(OC2H5)2; δB = 0 ppm). HR-MS MALDI spectra
were recorded on an ESP-MALDI-FT-ICR instrument equipped with a 7T magnet (prior to the
experiments, the instrument was calibrated using NaTFA cluster ions). IR spectra were recorded on a FT-
IR instrument using the attenuated total reflectance (ATR) sampling technique and the measurements
were carried out on a thin film of each sample obtained by evaporation from a solution of deuterated
chloroform or benzene. UV-Vis absorption measurements were performed in a 1-cm path-length cuvette
and the neat solvent was used as baseline; sh = shoulder. All melting points are uncorrected.
4-Bromo-2,6-dimethylphenyl trifluoromethanesulfonate: To a stirring solution of 4-bromo-2,6-xylenol
(1.98 g, 9.84 mmol) in dry pyridine (10 mL) cooled in an ice bath under an argon atmosphere was added
dropwise triflic anhydride (2 mL, 11.9 mmol). The cooling bath was removed and the contents of the
vessel were allowed to stir at ambient temperature for 16 h. The contents of the vessel were diluted with
Et2O (50 mL) and washed with aqueous 1M CuSO4 (3 x 50 mL). The organic phase was dried over
MgSO4, filtered and the crude oil purified by flash column chromatography (10% CH2Cl2/petroleum
spirit) to afford the title compound (2.23 g, 68%) as a colorless oil. Rf = 0.49 (10% CH2Cl2/petroleum
spirit). IR: 2977, 2931, 1606, 1571 cm-1. 1H NMR (500 MHz, CDCl3) δ = 7.28 (s, 2H), 2.36 (s, 6H) ppm.
13C NMR (125 MHz, CDCl3) δ = 145.9, 133.8, 132.7, 121.5, 118.7 (q, J = 320 Hz), 17.2 ppm. Anal.
Calcd (%) for C9H8BrF3O3S (333.12): C, 32.45; H, 2.42; Found: C, 32.60; H, 2.27. GCMS (EI) m/z (%):
[M, 79/81Br]•+ Calcd for [C9H8BrF3O3S]•+ 332 (100), 334 (97); Found: 332 (98), 334 (100).
2,6-Dimethyl-4-(trimethylsilyl)ethynyl)phenyl trifluoromethanesulfonate (1f): To a degassed solution
of 4-bromo-2,6-dimethylphenyl trifluoromethanesulfonate (1.08 g, 3.24 mmol), trimethylsilylacetylene
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(0.7 mL, 4.9 mmol) in diisopropylamine (30 mL) and THF (50 mL) were added Pd(PPh3)2Cl2 (124 mg,
0.177 mmol) and CuI (33 mg, 0.173 mmol), and the resulting mixture heated to 70 °C for 1 h under inert
atmosphere. The solvent was removed under reduced pressure and the residue subjected to flash column
chromatography (10% CH2Cl2/heptane) to give 1f (649 mg, 57%) as a colorless oil. Rf = 0.45 (10%
CH2Cl2/heptane). IR: 2963, 2901, 2161, 1592 cm-1. 1H NMR (500 MHz, CDCl3) δ = 7.23 (s, 2H), 2.35 (s,
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6H), 0.24 (s, 9H) ppm. C NMR (125 MHz, CDCl3) δ = 146.8, 133.4, 131.8, 123.3, 118.7 (q, J = 320
Hz), 103.4, 95.8, 17.1, 0.0 ppm. Anal. Calcd (%) for C14H17F3O3SSi (350.43): C, 47.99; H, 4.89; Found:
C, 47.72; H, 4.77. HRMS (MALDI +ve): m/z [M+Na]+ Calcd for [C14H17F3O3SSiNa]+ 373.0512; Found
373.0545.
2-(4-((Trimethylsilyl)ethynyl)phenyl)azulene-1-carbonitrile (1k): To a degassed solution of 2-(4-
iodophenyl)azulene-1-carbonitrile22 (463 mg, 1.30 mmol), trimethylsilylacetylene (1.0 mL, 7.0 mmol) in
Et3N (5 mL) and toluene (30 mL) were added Pd(PPh3)2Cl2 (55 mg, 0.078 mmol) and CuI (19 mg, 0.10
mmol) and the resulting mixture stirred overnight at ambient temperature under inert atmosphere. The
solvent was removed under reduced pressure and the residue subjected to column chromatography (90%
toluene/heptane) to give 1k (418 mg, 99%) as a dark purple solid. M.p. 158–159.5 °C. Rf = 0.38 (90%
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toluene/heptane). IR: 2958, 2898, 2202, 2155, 1604, 1590sh, 1577, 1537 cm-1. H NMR (500 MHz,
CDCl3) δ = 8.64 (dd, J = 9.8, 1.6 Hz, 1H), 8.40 (d, J = 9.8 Hz, 1H), 8.02 (d, J = 8.2 Hz, 2H), 7.79 (t, J =
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9.8 Hz, 1H), 7.61 (d, J = 8.3 Hz, 2H), 7.56–7.52 (m, 2H), 7.49 (t, J = 9.8 Hz, 1H), 0.28 (s, 9H) ppm. C
NMR (125 MHz, CDCl3) δ = 151.0, 145.9, 142.6, 139.3, 138.3, 136.1, 134.4, 132.8, 128.5, 128.3, 128.1,
124.3, 118.1, 116.6, 104.8, 96.7, 94.2, 0.1 ppm. Anal. Calcd (%) for C22H19NSi (325.49): C, 81.18; H,
5.88; N, 4.30; Found: C, 80.98; H, 5.95; N, 4.30. HRMS (MALDI +ve): m/z [M]•+ Calcd for
[C22H19NSi]•+ 325.1281; Found 325.1288. UV-Vis (CHCl3) λmax (ε): 632sh, 578 (6.83 x 102 M-1cm-1), 549
(6.60 x 102 M-1cm-1), 406sh, 391 (1.57 x 104 M-1cm-1), 331 (5.69 x 104 M-1cm-1), 292sh nm.
Alkynylation of SubPc-Cl
Compound 2a: To a stirring suspension of SubPc-Cl (50 mg, 0.12 mmol) and ((4-
methoxyphenyl)ethynyl)trimethylsilane (0.25 mL, 1.2 mmol) in o-dichlorobenzene (4 mL) was added
AlCl3 (76 mg, 0.58 mmol), and the resulting mixture was stirred for 15 h at rt. Pyridine (0.1 mL) was
added, and the reaction mixture was filtered through a short plug of neutral Brockman I Al2O3 using
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gradient elution from toluene to 10% EtOAc/toluene. The filtrate was concentrated in vacuo and
subjected to flash column chromatography (30% EtOAc/heptane) to furnish 2a (42 mg, 69%) as a golden
brown crystalline solid. Crystals suitable for X-ray crystallography were grown from CHCl3/heptane. Rf =
0.35 (5% EtOAc/toluene). M.p. >230 °C. IR: 3060, 3002, 2953, 2932, 2835, 2178, 1603, 1569, 1507 cm-
1. 1H NMR (500 MHz, CDCl3) δ 8.86 (dd, J = 5.9, 3.0 Hz, 6H), 7.89 (dd, J = 5.9, 3.0 Hz, 6H), 6.67 (d, J =
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9.1 Hz, 2H), 6.46 (d, J = 9.1 Hz, 2H), 3.61 (s, 3H) ppm. C NMR (126 MHz, CDCl3) δ 159.3, 150.6,
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133.0, 131.1, 129.7, 122.2, 114.7, 113.4, 94.2, 55.2 (1C missing) ppm. B NMR (160 MHz, CDCl3) δ -
21.3 ppm. Anal. Calcd (%) for C33H19BN6O (526.17): C, 75.30; H, 3.64; N, 15.97; Found: C, 74.96; H,
3.52; N, 16.10. HRMS (MALDI +ve): m/z [M+H]+ Calcd for [C33H20BN6O]+ 527.1786; Found 527.1792.
UV-Vis (CHCl3) λmax (ε): 568 (8.44 x 104 M-1cm-1), 550sh, 520sh, 308 (5.15 x 104 M-1cm-1), 269 (4.95 x
104 M-1cm-1) nm.
Compounds 2b-2k and 3-6 were prepared analogously to the above procedure.
Compound 2b (known compound9): Golden brown crystalline solid (68 mg, 89%). Reactants: SubPc-Cl
(53 mg, 0.12 mmol), (4-iodophenylethynyl)trimethylsilane (230 mg, 0.77 mmol), and AlCl3 (81 mg, 0.61
mmol). Rf = 0.34 (20% EtOAc/heptane). M.p. >230 °C. IR: 3059, 2922, 2850, 2182, 1613 cm-1. 1H NMR
(500 MHz, CDCl3) δ 8.86 (dd, J = 5.9, 3.0 Hz, 6H), 7.89 (dd, J = 5.9, 3.0 Hz, 6H), 7.27 (d, J = 8.7 Hz,
2H), 6.45 (d, J = 8.7 Hz, 2H) ppm. 13C NMR (126 MHz, CDCl3) δ 150.4, 136.8, 132.9, 130.9, 129.7,
122.1, 121.9, 93.7 (2C missing) ppm. 11B NMR (160 MHz, CDCl3) δ -21.3 ppm. Anal. Calcd (%) for
C32H16BIN6 (622.06): C, 61.77; H, 2.59; N, 13.51; Found: C, 61.85; H, 2.52; N, 13.44. HRMS (MALDI
+ve): m/z [M+H]+ Calcd for [C32H17BIN6]+ 623.0647; Found 623.0652. UV-Vis (CHCl3) λmax (ε): 569
(8.31 x 104 M-1cm-1), 551sh, 521sh, 308 (5.23 x 104 M-1cm-1), 531 (5.29 x 104 M-1cm-1) nm.
Compound 2c: Golden brown crystalline solid (50 mg, 88%). Reactants: SubPc-Cl (50 mg, 0.12 mmol),
trimethyl(phenylethynyl)silane (0.23 mL, 1.2 mmol), and AlCl3 (83 mg, 0.62 mmol). Rf = 0.27 (3%
EtOAc/toluene). M.p. >230 °C. IR: 3060, 2924, 2852, 2180, 1739, 1712, 1613, 1596, 1570, 1565 cm-1. 1H
NMR (500 MHz, CDCl3) δ 8.86 (dd, J = 5.9, 3.0 Hz, 6H), 7.89 (dd, J = 5.9, 3.0 Hz, 6H), 7.04–6.96 (m,
1H), 6.95–6.90 (m, 2H), 6.75–6.71 (m, 2H) ppm. 13C NMR (126 MHz, CDCl3) δ 150.6, 131.5, 131.0,
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129.8, 127.9, 127.8, 122.5, 122.2 (2C missing) ppm. B NMR (160 MHz, CDCl3) δ -21.2 ppm. HRMS
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(MALDI +ve): m/z [M+H]+ Calcd for [C32H18BN6]+ 497.1681; Found 497.1687. UV-Vis (CHCl3) λmax
(ε): 569 (9.61 x 104 M-1cm-1), 550sh, 525sh, 308 (5.90 x 104 M-1cm-1), 258 (5.08 x 104 M-1cm-1) nm.
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Compound 2d: Brown crystalline solid (19 mg, 28%). Reactants: SubPc-Cl (54 mg, 0.12 mmol), N,N-
dimethyl-4-((trimethylsilyl)ethynyl)aniline (262 mg, 1.21 mmol), and AlCl3 (88 mg, 0.66 mmol). Rf =
0.34 (30% EtOAc/heptane). M.p. >230 °C. IR: 3087, 3058, 2922, 2853, 2806, 2188, 2136sh, 1606, 1520
cm-1. 1H NMR (500 MHz, CDCl3) δ 8.85 (dd, J = 5.9, 3.0 Hz, 6H), 7.88 (dd, J = 5.9, 3.0 Hz, 6H), 6.61 (d,
J = 9.1 Hz, 2H), 6.24 (d, J = 9.1 Hz, 2H), 2.77 (s, 6H) ppm. 13C NMR (126 MHz, CDCl3) δ 150.6, 149.8,
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132.6, 131.1, 129.6, 122.2, 111.4, 109.4, 40.2 (2C missing) ppm. B NMR (160 MHz, CDCl3) δ -21.2
ppm. Anal. Calcd (%) for C34H22BN7 (539.20): C, 75.71; H, 4.11; N, 18.18; Found: C, 75.90; H, 3.95; N,
17.97. HRMS (MALDI +ve): m/z [M+H]+ Calcd for [C34H23BN7]+ 540.2103; Found 540.2109. UV-Vis
(CHCl3) λmax (ε): 568 (9.22 x 104 M-1cm-1), 550sh, 525sh, 306 (8.21 x 104 M-1cm-1) nm.
Compound 2e: Golden brown crystalline solid (65 mg, 86%). Reactants: SubPc-Cl (62 mg, 0.14 mmol),
4-((trimethylsilyl)ethynyl)benzonitrile (230 mg, 1.15 mmol), and AlCl3 (232 mg, 1.74 mmol). Rf = 0.32
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(25% EtOAc/heptane). M.p. >230 °C. IR: 3087sh, 3060, 2227, 2185, 1613, 1602, 1567 cm-1. H NMR
(500 MHz, CDCl3) δ 8.86 (dd, J = 5.8, 3.0 Hz, 6H), 7.90 (dd, J = 5.8, 3.0 Hz, 6H), 7.23 (d, J = 8.5 Hz,
2H), 6.81 (d, J = 8.5 Hz, 2H) ppm. 13C NMR (126 MHz, CDCl3) δ 150.4, 131.8, 131.4, 130.8, 129.8,
127.4, 122.1, 118.3, 111.0, 92.4 (1C missing) ppm. 11B NMR (160 MHz, CDCl3) δ -21.3 ppm. Anal.
Calcd (%) for C33H16BN7 (521.16): C, 76.03; H, 3.09; N, 18.81; Found: C, 76.12; H, 3.03; N, 18.71.
HRMS (MALDI +ve): m/z [M+H]+ Calcd for [C33H17BN7]+ 522.1633; Found 522.1641. UV-Vis (CHCl3)
λmax (ε): 570 (8.82 x 104 M-1cm-1), 552sh, 525sh, 308 (5.74 x 104 M-1cm-1), 526 (5.87 x 104 M-1cm-1) nm.
Compound 2f: Golden brown crystalline solid (83 mg, 93%). Reactants: SubPc-Cl (57 mg, 0.13 mmol),
1f (469 mg, 1.34 mmol), and AlCl3 (88 mg, 0.66 mmol). Rf = 0.36 (25% EtOAc/heptane). M.p. >230 °C.
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IR: 3060, 2970, 2930, 2182, 1614, 1592 cm-1. H NMR (500 MHz, CDCl3) δ 8.86 (dd, J = 5.9, 3.0 Hz,
6H), 7.89 (dd, J = 5.9, 3.0 Hz, 6H), 6.51 (s, 2H), 2.06 (s, 6H) ppm. 13C NMR (126 MHz, CDCl3) δ 150.4,
146.1, 132.6, 131.1, 130.9, 129.7, 122.4, 122.2, 122.1, 119.7, 117.1, 114.6, 92.5, 16.6 (1C missing) ppm.
11B NMR (160 MHz, CDCl3) δ -21.3 ppm. Anal. Calcd (%) for C35H20BF3N6O3S (672.14): C, 62.52; H,
3.00; N, 12.50; Found: C, 62.60; H, 2.85; N, 12.53. HRMS (MALDI +ve): m/z [M+H]+ Calcd for
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[C35H21BF3N6O3S]+ 673.1435; Found 673.1441. UV-Vis (CHCl3) λmax (ε): 569 (7.99 x 104 M-1cm-1),
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553sh, 525sh, 308 (4.95 x 104 M-1cm-1), 261 (4.18 x 104 M-1cm-1) nm.
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Compound 2g: Deep purple shiny crystalline solid (39.0 mg, 65%). Reactants: SubPc-Cl (53 mg, 0.12
mmol), (trimethylsilylethynyl)trimethylsilane (214 mg, 1.26 mmol), and AlCl3 (99 mg, 0.74 mmol). Rf =
0.34 (20% EtOAc/heptanes). M.p. >230 °C. IR: 2951, 2917, 2849, 2361, 2338 cm-1. 1H NMR (500 MHz,
CDCl3) δ 8.85 (dd, J = 5.9, 3.1 Hz, 6H), 7.88 (dd, J = 5.9, 3.1 Hz, 6H), -0.37 (s, 9H) ppm. 13C NMR (126
MHz, CDCl3) δ 150.6, 131.0, 129.7, 128.5, 122.2, 101.3, -0.3 ppm. Anal. calcd (%) for C29H21BN6Si
(492.41): C, 70.74; H, 4.30; N, 17.07. Found: C, 70.58; H, 4.39; N, 16.96. HRMS (MALDI +ve): m/z
[M+H]+ Calcd for [C29H22BN6Si]+ 493.1763; Found 493.1770. UV-Vis (CHCl3) λmax (ε): 569 (8.91 x 104
M-1cm-1), 552sh, 527sh, 308 (5.49 x 104 M-1cm-1), 272sh nm.
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Compound 2h: Bright pink solid (85 mg, 97%). Reactants: SubPc-Cl (73 mg, 0.170 mmol), 1,4-
bis(trimethylsilyl)buta-1,3-diyne (303 mg, 1.56 mmol), and AlCl3 (145 mg, 1.09 mmol). Rf = 0.35
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(EtOAc/heptane 1:3). M.p. >230 °C. IR: 3062, 2959, 2079, 1614 cm-1. H NMR (500 MHz, CDCl3) δ =
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8.84 (dd, J = 6.0, 3.0 Hz, 6H), 7.88 (dd, J = 6.0, 3.0 Hz, 6H), -0.08 (s, 9H) ppm. C NMR (125 MHz,
CDCl3) δ = 150.4, 130.9, 129.9, 122.3, 87.5, 84.7, -0.6 (2C missing) ppm. 11B NMR (160 MHz, CDCl3) δ
= -21.8 ppm. Anal. Calcd (%) for C31H21BN6Si (516.45): C, 72.10; H, 4.10; N, 16.27; Found: C, 71.94;
H, 4.02; N, 16.50. HRMS (MALDI +ve): m/z [M+H]+ Calcd for [C31H22BN6Si]+ 517.1763; Found
517.1770. UV-Vis (CHCl3) λmax (ε): 570 (8.53 x 104 M-1cm-1), 552sh, 526sh, 308 (5.27 x 104 M-1cm-1),
278sh nm.
Compound 2i (known compound8): Bright purple solid (93 mg, 89%). In addition, recovered 1i (378 mg,
78%) was isolated. Reactants: SubPc-Cl (74 mg, 0.172 mmol), 1i (486 mg, 1.72 mmol), and AlCl3 (142
mg, 1.06 mmol). Rf = 0.39 (25% EtOAc/heptane). M.p. >230 °C. IR: 3088, 3059, 2924, 2184, 2170sh,
1613 cm-1. 1H NMR (500 MHz, CDCl3) δ = 8.87 (dd, J = 5.9, 3.0 Hz, 6H), 7.89 (dd, J = 5.9, 3.0 Hz, 6H),
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3.82 (t, J = 1.9 Hz, 2H), 3.78 (s, 5H), 3.76 (t, J = 1.9 Hz, 2H) ppm. B NMR (160 MHz, CDCl3) δ = -
21.4 ppm. HRMS (MALDI +ve): m/z [M]•+ Calcd for [C36H21BFeN6]•+ 604.1265; Found 604.1272.
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Compound 2j: Bright purple solid (72 mg, 57%). In addition, the triad 3 (8 mg, 4%) was isolated as a
dark purple solid as well as recovered 1j (327 mg, 51%). Reactants: SubPc-Cl (78 mg, 0.181 mmol), 1j
(644 mg, 1.70 mmol), and AlCl3 (137 mg, 1.03 mmol). Rf = 0.31 (25% EtOAc/heptane). M.p. >230 °C.
IR: 3086, 3058, 2957, 2895, 2184, 2164, 2149, 1614 cm-1. 1H NMR (500 MHz, CDCl3) δ = 8.86 (dd, J =
5.9, 3.1 Hz, 6H), 7.88 (dd, J = 5.9, 3.1 Hz, 6H), 4.06 (t, J = 1.9 Hz, 2H), 3.85 (t, J = 1.9 Hz, 2H), 3.77 (t, J
= 1.9 Hz, 2H), 3.73 (t, J = 1.9 Hz, 2H), 0.11 (s, 9H) ppm. 13C NMR (125 MHz, CDCl3) δ = 150.5, 131.0,
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129.7, 122.2, 103.5, 92.2 (br), 91.0, 73.1, 72.8, 71.7, 71.5, 65.5, 65.3, 0.3 (1C missing) ppm. B NMR
(160 MHz, CDCl3) δ = -21.3 ppm. HRMS (MALDI +ve): m/z [M]•+ Calcd for [C41H29BFeN6Si]•+
700.1660; Found 700.1667. UV-Vis (CHCl3) λmax (ε): 568 (8.34 x 104 M-1cm-1), 552sh, 525sh, 306 (5.35
x 104 M-1cm-1), 272sh nm.
Compound 2k: Deep purple solid (51 mg, 67%). In addition, recovered 1k (248 mg, 82%) was isolated.
Reactants: SubPc-Cl (50 mg, 0.12 mmol), 1k (301 mg, 0.925 mmol), and AlCl3 (186 mg, 1.39 mmol). Rf
= 0.27 (5% EtOAc / toluene). M.p. >230 °C. IR: 2917, 2849, 2204, 2178, 1738, 1611, 1605, 1575 cm-1.
1H NMR (500 MHz, C6D6) δ 8.78 (dd, J = 5.9, 3.1 Hz, 6H), 8.23 (d, J = 9.8 Hz, 1H), 7.54 (d, J = 9.8 Hz,
1H), 7.50 (d, J = 8.7 Hz, 2H), 7.40 (dd, J = 5.9, 3.1 Hz, 6H), 6.86 (t, J = 9.8 Hz, 1H), 6.75 (s, 1H), 6.72
(d, J = 8.7 Hz, 2H), 6.60 (t, J = 9.8 Hz, 1H), 6.58 (t, J = 9.8 Hz, 1H) ppm. 13C NMR (126 MHz, C6D6) δ
151.0, 150.6, 145.37, 141.9, 138.0, 137.3, 135.6, 133.8, 132.4, 131.7, 129.5, 127.2, 127.0, 124.1, 122.1,
117.2, 116.6, 95.3, 94.6 ppm. Anal. calcd (%) for C43H22BN7 (647.51): C, 79.76; H, 3.42; N, 15.14;
Found: C, 79.83; H, 3.39; N, 14.92. HRMS (MALDI +ve): m/z [M+H]+ Calcd for [C43H23BN7]+
648.2103; Found 648.2112. UV-Vis (CHCl3) λmax (ε): 569 (8.25 x 104 M-1cm-1), 552sh, 526sh, 409sh, 393
(1.99 x 104 M-1cm-1), 331 (6.58 x 104 M-1cm-1), 311 (7.85 x 104 M-1cm-1) nm.
Compound 3: Dark purple solid (20 mg, 8%). Reactants: SubPc-Cl (100 mg, 0.232 mmol), 1j (48 mg,
0.13 mmol), and AlCl3 (88 mg, 0.66 mmol). Rf = 0.54 (5% EtOAc/CH2Cl2). M.p. >230 °C. IR: 3063,
2184, 1613 cm-1. 1H NMR (500 MHz, CDCl3) δ = 8.82 (dd, J = 5.9, 3.0 Hz, 12H), 7.87 (dd, J = 5.9, 3.0
Hz, 12H), 3.48 (d, J = 1.9 Hz, 4H), 3.31 (d, J = 1.9 Hz, 4H) ppm. 13C NMR (125 MHz, CDCl3) δ = 150.5,
131.0, 129.7, 122.2, 77.7, 71.8, 71.7 (2C missing) ppm. 11B NMR (160 MHz, CDCl3) δ = -21.5 ppm.
Anal. Calcd (%) for C62H32B2FeN12 (1022.49): C, 72.83; H, 3.15; N, 16.44; Found: C, 72.79; H, 2.94; N,
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16.28. HRMS (MALDI +ve): m/z [M]•+ Calcd for [C62H32B2FeN12]•+ 1022.2403; Found 1022.2412. UV-
Vis (CHCl3) λmax (ε): 567.5 (1.36 x 105 M-1cm-1), 550sh, 518sh, 307 (8.87 x 104 M-1cm-1) nm.
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Compound 4: Brown crystalline solid (42 mg, 76%). Reactants: SubPc-Cl (54 mg, 0.12 mmol),
allyltrimethylsilane (0.20 mL, 1.2 mmol), and AlCl3 (88 mg, 0.66 mmol). Rf = 0.31 (20%
EtOAc/toluene). M.p. >230 °C. IR: 3061, 2966, 2913, 2869, 1726, 1628, 1612, 1584 cm-1. 1H NMR (500
MHz, CDCl3) δ 8.82 (dd, J = 5.9, 3.0 Hz, 6H), 7.86 (dd, J = 5.9, 3.0 Hz, 6H), 4.20–4.08 (m, 2H), 3.83–
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3.74 (m, 1H), -1.16 (d, J = 5.6 Hz, 2H) ppm. C NMR (126 MHz, CDCl3) δ 151.1, 133.3, 130.9, 129.6,
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122.1, 113.6, 25.3 ppm. B NMR (160 MHz, CDCl3) δ -15.8 ppm. HRMS (MALDI +ve): m/z [M+H]+
Calcd for [C27H18BN6]+ 437.1681; Found 437.1687. UV-Vis (CHCl3) λmax (ε): 566 (8.83 x 104 M-1cm-1),
549sh, 522sh, 311 (4.54 x 104 M-1cm-1) nm.
Compound 5 (known compound8): Bright purple solid (50 mg, 50%). In addition, recovered ferrocene
(230 mg, 75%) was isolated. Reactants: SubPc-Cl (74 mg, 0.172 mmol), ferrocene (305 mg, 1.64 mmol),
and AlCl3 (145 mg, 1.09 mmol). Rf = 0.39 (25% EtOAc/heptane). M.p. >230 °C. IR: 3087, 3059, 1613
cm-1. 1H NMR (500 MHz, CDCl3) δ = 8.86 (dd, J = 5.9, 3.1 Hz, 6H), 7.89 (dd, J = 5.9, 3.1 Hz, 6H), 3.56
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(s, 5H), 3.50 (t, J = 1.8 Hz, 2H), 2.37 (t, J = 1.8 Hz, 2H) ppm. B NMR (160 MHz, CDCl3) δ = -16.1
ppm. HRMS (MALDI +ve): m/z [M]•+ Calcd for [C34H21BFeN6]•+ 580.1265; Found 580.1272.
Compound 6: Bright pink solid (12 mg, 12%). Reactants: SubPc-Cl (78 mg, 0.181 mmol), 1,2,3-
trimethoxybenzene (297 mg, 1.77 mmol), and AlCl3 (142 mg, 1.06 mmol). Rf = 0.30 (33%
EtOAc/heptane). M.p. >230 °C. IR: 3059, 2956, 2927, 2853, 2834, 1727, 1614, 1594 cm-1. 1H NMR (500
MHz, CDCl3) δ = 8.83 (dd, J = 5.9, 3.0 Hz, 6H), 7.87 (dd, J = 5.9, 3.0 Hz, 6H), 6.55 (t, J = 8.3 Hz, 1H),
6.03 (d, J = 8.3 Hz, 2H), 3.23 (s, 6H) ppm. 13C NMR (125 MHz, CDCl3) δ = 152.1, 150.8, 131.2, 129.6,
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122.2, 122.0, 104.4, 55.5 (1C missing) ppm. B NMR (160 MHz, CDCl3) δ = -15.3 ppm. Anal. Calcd
(%) for C32H21BN6O3 (548.37): C, 70.09; H, 3.86; N, 15.33. Found: C, 70.11; H, 3.93; N, 15.41. HRMS
(MALDI +ve): m/z [M+H]+ Calcd for [C32H22BN6O3]+ 549.1841; Found 549.1849. UV-Vis (CHCl3) λmax
(ε): 564 (8.63 x 104 M-1cm-1), 546sh, 522sh, 304 (3.71 x 104 M-1cm-1), 269 (3.50 x 104 M-1cm-1) nm.
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Supporting Information
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The Supporting Information contains NMR and UV-Vis absorption spectra as well as X-ray crystal
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structures of 2i and 5 and is available free of charge on the ACS Publications website at DOI: ######
Author Information
Corresponding Author
*E-mail: mbn@chem.ku.dk
Notes
The authors declare no competing financial interest.
Acknowledgments
University of Copenhagen is acknowledged for financial support.
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16
ACS Paragon Plus Environment