Organometallics
Article
−CH(CH3) (CH3)], 0.77 [3H, d, −CH(CH3)(CH3)]. 13C{1H} NMR
(CDCl3): δ 164.65 (CN), 133.62−122.05 (PhC), 73.38, 73.13 (C
C), 68.31 (−CHCH2), 65.89 (−CHCH2), 70.67, 70.51 (CpC), 30.13
[−H(CH3)2], 19.04, 14.18 [−CH(CH3)2].
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
Synthesis of {Fc-CC-C6H4-o-(4-Ph-2-Ox)CuI}(4c). Fc−CC−Cu
(65.6 mg, 0.240 mmol), 2c (70 mg, 0.200 mmol), [(PPh3)2PdCl2] (15
mg, 10 mol %). Red solid. Yield: 66 mg, 0.106 mmol, 53%. Mp: 74−75
°C (dec). [α]25D = +135.14 (c 0.074, CH2Cl2). Anal. Found: C, 52.25;
H, 3.37; N, 2.22. Calcd for C27H21CuNOFeI: C, 52.16; H, 3.40; N,
Experimental data and tables giving selected bond
lengths and angles and crystallographic data for
1
2.25. IR (ν, cm−1): 1990.74 (coordinated CC). H NMR: δ 7.12−
Crystallographic data for compounds 4a−c (CIF)
8.36 [4H + 5H, 2d, 2t, m Ph-H], 5.81 [1H, dd, CHPh−], 4.59 [2H, m,
−Ox−CH2], 4.24−4.41 [9H, Fc]. 13C{1H} NMR (CDCl3): δ 164.59
(CN), 137.45−125.42 (PhC), 73.84, 70.79 (CC), 70.66−69.93
(CpC), 68.86−68.56 [Ox−CH2], 64.23 [CHPh].
AUTHOR INFORMATION
Corresponding Author
Notes
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General Procedure of Synthesis of Metal-Free Cu(I) Specific
Ligands (5a,b). An oven-dried two-necked round-bottom flask was
charged with the π-copper complexes 4a−c under nitrogen, which
were dissolved in 10−15 mL of DMF. Excess (10 mL) aqueous
ammonia solution was added to it, and the mixture was stirred for
about a minute. The reaction mixture was fractionated using 50 mL of
water and 50 mL of ethyl acetate. The organic layer was washed (5 ×
50 mL) with water. The organic layer was dried over anhydrous
Na2SO4, filtered, evaporated, and purified by column chromatography
using silica gel with a 2% ethyl acetate/hexane mixture as eluent.
Synthesis of {Fc-CC-C6H4-o-(4-iPr-2-Ox)} (5a). 4a (300 mg,
0.511 mmol) was dissolved in DMF, and aqueous NH3 was added.
The product was purified as mentioned in procedure E. Yellow
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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The authors thank DST, India, and CSIR, India, for financial
assistance in the form of research grants to A.J.E [DST EMR/
2015/000285, CSIR 01(2693)/12/EMR-II]. M.D. and J.S.
thank UGC and D.K. thanks CSIR for fellowships. We thank
DST-FIST and IITD for funding the single-crystal X-ray and
HRMS facilities at IIT Delhi.
semisolid. Yield: 202 mg, 0.506 mmol, 99%. [α]25 = −58.11 (c
D
REFERENCES
0.00074, CH2Cl2). IR (ν, cm−1): 2251, (CC). 1H NMR (CDCl3): δ
7.83−7.80 [1H, d, Ph−H], 7.6−7.57 [1H, d, Ph−H], 7.4−7.28 [2H,
m, Ph−H], 4.52−4.45 [3H, m, Ox−CH2−], 4.27−4.24 [7H, s, α
protons of C5H4 + C5H5 of Fc], 4.22−4.19 [2H, m, β protons of C5H4
of Fc], 2.00−1.9 [1H, m, −CH(CH3)2], 1.13−1.09 [3H, d,
−CH(CH3) (CH3)], 1.02−1.00 [3H, d, −CH(CH3)(CH3)].
13C{1H} NMR (CDCl3): δ 163.42 (CN), 133.47−123.49 (PhC),
73.38, 73.00−71.42 (CC), 70.17, 68.86 (CpC), 68.17 (−CHCH2),
65.50 (−CHCH2), 28.94 [−CH(CH3)2], 19.00, 18.34 [−CH(CH3)2].
HRMS: calcd m/z for C24H24NOFe [M + H]+ 398.1202; found
398.1209.
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Synthesis of {Fc-CC-C6H4-o-(4-Ph-2-Ox)} (5b). 4c (125 mg,
0.201 mmol) was dissolved in DMF, and aqueous NH3 was added.
The product was purified as mentioned in procedure E. Yellow
semisolid. Yield: 83 mg, 0.191 mmol, 95%. [α]25 = −30.76 (c
D
0.00026, CH2Cl2). IR (ν, cm−1): 2258 (CC). 1H NMR (CDCl3): δ
7.85−7.83 [1H, d, Ph−H], 7.55−7.53 [1H, d, Ph−H], 7.4−7.28 [7H,
m, Ph−H], 5.41 [1H, dd, CHPh−], 4.79 [1H, dd, Ox−CH2−], 4.37−
4.13 [10H, 1H, dd, Ox−CH2− + all protons of Fc]. 13C{1H} NMR
(CDCl3): δ 164.84 (CN), 142.58−123.69 (PhC), 74.90, 71.52 (C
C), 69.93−68.91 (CpC), 68.86−68.56 [Ox−CH2], 65.29 [CHPh].
HRMS: calcd m/z for C27H22NOFe [M + H]+ 432.1045; found
432.1046.
Crystal Structure Determination. Suitable crystals of com-
pounds 4a−c were obtained by slow evaporation of their saturated
solutions in suitable solvent mixtures. Single-crystal diffraction studies
were carried out on a Bruker SMART APEX CCD diffractometer with
a Mo Kα (λ = 0.710 73 Å) sealed tube. All crystal structures were
solved by direct methods. The program SAINT (version 6.22) was
used for integration of the intensity of reflections and scaling. The
program SADABS was used for absorption correction. The crystal
structures were solved and refined using the SHELXTL (version 6.12)
package.15 All hydrogen atoms were included in idealized positions,
and a riding model was used. Non-hydrogen atoms were refined with
anisotropic displacement parameters. Table S7 lists the data collection
and structure solving parameters for compounds 4a−c (see
S5, and S6).
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Organometallics XXXX, XXX, XXX−XXX