Inorganic Chemistry
ARTICLE
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General Procedure for the Synthesis of Copper(I) Complexes
C1ꢀC6. Cu(CH3CN)4PF6 was dissolved in distilled dichloromethane
and thoroughly degassed by a few vacuum/argon cycles. An argon
purged solution of mesityl bearing ligand phenA (L1 or Mes-phen; 1.0
equivalent) in dichloromethane was then syringed into the former
solution, and the mixture was stirred at room temperature. After 5
min, an argon purged solution of ligand phenB (1.0 equivalent, phenB =
phen, Me-phen, nBu-phen, or L2) in dichloromethane was syringed into
the yellow mixture. The latter immediately turned deep red and was left
to stir for half an hour at room temperature. The solvent was then
removed by rotary evaporation. The red residue was eventually purified
by chromatography on silica gel. Reactions were all performed at least
three times, and yields were all comprised between 75 and 85%. In what
follows, H nuclei belonging to phenB (nonmesityl derivatized) are
primed.
H3 and H8), 7.51 (d, 2H, H3 and H8 ), 6.20 (s, 4H, Hmes,arom), 2.31
(m, 4H, CH2,butyl), 1.91 (s, 6H, CH3,mes), 1.54 (s, 12H, CH3,mes), 1.16
(m, 4H, CH2,butyl), 0.81 (m, 4H, CH2,butyl), 0.67 (m, 6H, CH3,butyl).
HR-MS (m/z): 771.3489 [M ꢀ PF6]+. Anal. for C6 CH3OH H2O.
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Found (%): C, 63.31; H, 6.08; N, 5.44. Calcd: C, 63.31; H, 6.04; N, 5.79.
Complex C7. In a Schlenk tube fitted with a water condenser, C2
(27 mg, 0.024 mmol) and p-methoxyphenyl boronic acid (19 mg, 0.13
mmol) were dissolved in 4 mL of a 9:1 (v/v) mixture of 1,2-dimethox-
yethane (DME) and water, respectively. Barium hydroxide (50 mg, 0.29
mmol) was then added. The setup was thoroughly degassed with argon,
and palladium tetrakis triphenylphosphine (3 mg, 0.003 mmol) was
quickly added. The mixture was heated to 110 °C and stirred for 16 h,
under argon. It was then allowed to cool down to room temperature, and
water was added. The orange suspension was extracted three times with
dichloromethane. The organic layers were gathered, dried on sodium
sulfate, and evaporated under reduced pressure. The product was puri-
fied by column chromatography on silica gel and eluted with a gradient
of methanol in dichloromethane (from 2% to 10%) to yield a red
powder. Yield: 9 mg, 34%. 1H NMR (300 MHz, CDCl3, 25 °C): δ 15.30
(s broad, 1H, Himidazole), 10.46 (s broad, 1H, H4 or H7), 9.40 (d, 1H, H7
C1: obtained with phenA = L1, phenB = Me-phen. 1H NMR (300 MHz,
CDCl3, 25 °C): δ 11.92 (s, 1H, Himidazole), 9.45 (d, 1H, H4 or H7), 9.36
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(d, 1H, H7 or H4), 8.34 (d, 2H, H11 and H14), 8.22 (d, 2H, H4 and H7 ),
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7.82 (d, 2H, H12 and H13), 7.79 0(s, 2H, H5 and H6 ), 7.72 (d, 2H, H3
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and H8), 7.49 (d, 2H, H3 and H8 ), 6.11 (s, 2H, Hmes,arom), 6.02 (s, 2H,
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H
mes,arom), 2.21 (s, 6H, CH3,methyl), 1.76 (s, 3H, CH3,mes), 1.73 (s, 3H,
or H4),0 8.88 (d, 2H, H11 and H14), 8.22 (d, 2H, H4 and H7 ), 7.77 (m,
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CH3,mes), 1.63 (s, 6H, CH3,mes), 1.56 (s, 6H, CH3,mes). HR-MS (m/z):
6H, H5 , H6 , H30, H8, H12 and H13), 7.63 (d, 2H, H15 and H18), 7.46 (d,
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881.2021 [M-PF6]+. Anal. for C1 CH3OH. Found (%): C, 58.73; H,
2H, H3 and H8 ), 7.00 (d, 2H, H16 and H17), 6.20 (s, 2H, Hmes,arom),
6.11 (s, 2H, Hmes,arom), 3.88 (s, 3H, OCH3), 2.35 (m, 4H, CH2,butyl),
1.90 (s, 3H, CH3,mes), 1.86 (s, 3H, CH3,mes), 1.57 (s, 6H, CH3,mes), 1.49
(s, 6H, CH3,mes), 1.18 (m, 4H, CH2,butyl), 0.82 (m, 4H, CH2,butyl), 0.62
(t, 6H, CH3,butyl). HR-MS (m/z): 993.4243 [M ꢀ PF6]+.
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4.28; N, 7.91. Calcd: C, 58.90; H, 4.47; N, 7.93.
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C2: obtained with phenA = L1, phenB = nBu-phen. H NMR (300
MHz, CDCl3, 25 °C): δ 11.97 (s, 1H, Himidazole), 9.37 (m, 2H, H4
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and H7), 8.31 (d, 2H, H11 and H14), 8.27 (d, 2H, H4 and H7 ), 7.83 (s, 2H,
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H5 and H6 ), 7.78 (d, 2H, H12 and H13), 7.65 (d, 2H, H3 and H8), 7.48
Complex C8. In a Schlenk tube fitted with a water condenser, C3
(25 mg, 0.022 mmol) and p-methoxyphenyl boronic acid (18 mg,
0.12 mmol) were dissolved in 2 mL of a 9:1 (v/v) mixture of 1,2-dimeth-
oxyethane (DME) and water, respectively. Barium hydroxide (39 mg,
0.23 mmol) was then added. The setup was thoroughly degassed with
argon, and palladium tetrakis triphenylphosphine (5 mg, 0.004 mmol)
was quickly added. The mixture was heated to 110 °C and stirred for
16 h, under argon. It was then allowed to cool down to room tempera-
ture, and water was added. The orange suspension was extracted three
times with dichloromethane. The organic layers were gathered, dried on
sodium sulfate, and evaporated under reduced pressure. The product
was purified by column chromatography on silica gel and prepared with
CH2Cl2/CH3OH (= 94:6) to yield a red powder.
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(d, 2H, H3 and H8 ), 6.22 (s, 2H, Hmes,arom), 6.11 (s, 2H, Hmes,arom),
2.33 (m, 4H, CH2,butyl), 1.91 (s, 3H, CH3,mes), 1.85 (s, 3H, CH3,mes),
1.58 (s, 6H, CH3,mes), 1.49 (s, 6H, CH3,mes), 1.18 (m, 4H, CH2,butyl),
0.80 (m, 4H, CH2,butyl), 0.61 (t, 6H, CH3,butyl). HR-MS (m/z):
965.2970 [M ꢀ PF6]+. Anal. for C2 1/2CH3OH. Found (%): C,
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61.21; H, 4.85; N, 7.28. Calcd: C, 61.20; H, 5.09; N, 7.26.
C3: obtained with phenA = Mes-phen, phenB = L2. H NMR (300
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MHz, CDCl3, 25 °C): δ 9.56 (m, 2H, H4 and H7 ), 8.76 (d, 2H, H4 and
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H7)0, 8.60 (d, 1H, H13 ), 8.28 (m, 3H, H5, H6 and H11 ),0 8.04 (dd, 1H,
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12 ), 7.79 (d, 2H, H3 and H8), 7.71 (m, 2H, H3 and H8 ), 6.19 (s, 2H,
mes,arom), 6.17 (s, 2H, Hmes,arom), 2.38 (m, 4H, CH2,butyl), 1.72 (s, 6H,
CH3,mes), 1.62 (s, 6H, CH3,mes), 1.60 (s, 6H, CH3,mes), 1.24 (m, 4H,
CH2,butyl), 0.84 (m, 4H, CH2,butyl), 0.70 (m, 6H, CH3,butyl). HR-MS
Yield: 21 mg, 84%. 1H NMR (300 MHz, CDCl3, 25 °C): δ 9.59 (2d,
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2H, H4 and H7 ), 8.76(d, 2H, H4 and H7), 8.55 (d, 1H, H13 ), 8.43 (d,
(m/z) 953.2801 [M ꢀ PF6]+. Anal. for C3 CH3OH. Found (%): C,
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1H, H11 ), 8.28 (m, 3H, H5, H6 and H12 ), 07.86 (d, 02H, H14 and H17 ),
60.63; H, 4.86; N, 7.34. Calcd: C, 60.56; H, 5.08; N, 7.43.
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7.79 (d, 02H, H3 and H8), 7.68 (2d, 2H, H3 and H8 ), 7.13 (d, 2H, H15
and H16 ), 6.19 (s, 4H, Hmes,arom), 3.94 (s, 3H, OCH3), 2.39 (m, 4H,
CH2,butyl), 1.74 (s, 6H, CH3,mes), 1.62 (s, 12H, CH3,mes), 1,25 (m, 4H,
CH2,butyl), 0.85 (m, 4H, CH2,butyl), 0.70 (m, 6H, CH3,butyl). HR-MS
(m/z): 979.4152 [M-PF6]+.
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C4: obtained with phenA = L1, phenB = L2. H NMR (300 MHz,
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CDCl3, 25 °C): δ 9.57 (d, 1H, H4 or H7 ), 9.55 (d, 1H, H7 or H4 ), 9.45
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(d, 2H, H4 and H7), 8.64 (d, 1H, H13 ), 8.38 (d, 2H, H11 and H14), 8.31
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(d, 1H, H11 ), 8.08 (dd, 1H, H120 ), 7.82 (0d, 2H, H3 and H8), 7.74 (d, 2H,
H
12 and H13), 7.65 (m, 2H, H3 and H8 ), 6.17 (s, 2H, Hmes,arom), 6.15
(s, 2H, Hmes,arom), 2.40 (m, 4H, CH2,butyl), 1.72 (s, 6H, CH3,mes), 1.62
(s, 6H, CH3,mes), 1.60 (s, 6H, CH3,mes), 1.25 (m, 4H, CH2,butyl), 0.84
(m, 4H, CH2,butyl), 0.64 (m, 6H, CH3,butyl). HR-MS (m/z): 1145.2266
Crystal Structure Data for C56H53BrCuN6 PF6 (ClCH3)0.629.
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Structure data are as follows: Mw = 1130.2, colorless block, 0.4 ꢁ 0.2 ꢁ
0.15 mm3, triclinic, P1, a = 13.6027(6) Å, b = 14.2161(14) Å, c =
15.4400(5) Å, α = 73.945(6)°, β = 83.606(6)°, γ = 85.364(7)°, V =
2847.5(3) Å3, Z = 2, Dx = 1.318 g cmꢀ3, μ = 1.2 mmꢀ1. A total of 82 229
reflections were measured on a Nonius-Kappa CCD diffractometer
[M ꢀ PF6]+. Anal. for C4 2CH3OH. Found (%): C, 57.43; H, 4.56; N,
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8.02. Calcd: C, 57.51; H, 4.75; N, 8.25.
C5: obtained with phenA = L1, phenB = Phen. Data for complex C5:
1H NMR (300 MHz, CDCl3, 25 °C): δ 9.36 (d, 2H, H4 and H7), 8.50
(graphite monochromator, λ= 0.71073 Å) up to a resolution of (sin θ/λ)max
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(d, 2H, H2 and H9 ), 8.39 (d, 2H, H4 and H7 ), 8.32 (d, 2H, H11 and
0.66 Åꢀ1 at 100 K. A total of 13 612 reflections were unique (Rint
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H14), 7.86 (s, 2H, H50 and H6 ), 7.82 (d, 2H, H12 and H13), 7.70 (m, 4H,
0.10). The structure was solved using the charge flipping algorithm31
implemented in the Superflip program32 and refined with the JANA2006
program33 against F2 forall reflections. A disorder intheL2 moiety, i.e., the
superposition of the two regioisomers, was correctly modeled using a rigid
body approach. However, the solvent molecules occupying the large void
(>200 Å) could not be determined; only two chloromethane solvent
molecules with a partial occupancy ratio were identified. Obviously,
the solvent molecules are disordered correlatively with the L2 moiety.
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H3, H8, H3 and H8 ), 5.88 (s, 4H, Hmes,arom), 1.70 (s, 12H, CH3,mes),
1.53 (s, 6H, CH3,mes). HR-MS (m/z): 853.1721 [M-PF6]+. Anal. for
C5 CH3OH. Found (%): C, 58.15; H, 4.17; N, 7.84. Calcd.: C, 58.17;
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H, 4.20; N, 8.14.
C6: obtained with phenA = Mes-phen, phenB = nBu-phen. 1H NMR
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(300 MHz, CDCl3, 25 °C): δ 8.70 (d, 2H, H4 and H7), 8.31 (d, 2H, H4
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and H7 ), 8.24 (s, 2H, H5 and H6), 7.85 (s, 2H, H5 and H6 ), 7.76 (d, 2H,
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dx.doi.org/10.1021/ic2006343 |Inorg. Chem. 2011, 50, 11309–11322