6
Journal of Organometallic Chemistry
yellowish powder. Our attempts to growing X-ray quality
atoms were refined anisotropically using SHELX [29]. The
coordinates of the hydrogen atoms were calculated from
geometrical positions (except for 9, the mixed method was used).
Within 7, the hexane molecule is disordered over two sites, each
in 50% occupancy (refined isotropically). Within 9, the
C(1A)Cl(1A)Cl(2A) molecule is disordered over two sites at
50:50 probability.
crystals of 11 from usual solvent systems were unsuccessful.
4.5. Characterization data for complexes 5-11
[Cu(2-Py3P=O)Cl]·0.5CH2Cl2 (5). Garnet crystals, > 150 oC dec.
Yield: 45 mg (88%). Н NMR (400.13 MHz, CDCl3, ppm), δ:
5.31 (s, 2H, CH2Cl2), 7.53 (t, JHH = 6.5 Hz, 3H, Py), 7.94-7.99
1
3
3
4
(m, 3H, Py), 8.40 (t, JHH = 7.0 Hz, 3H, Py), 9.03 (d, JPH = 4.7
Hz, 3H, Py). 31Р NMR (161.98 MHz, CDCl3, ppm), δ: –9.45.
UV-Vis (CHCl3, λmax/nm): 259, 342, 447. Anal. Calcd for
C15H12ClCuN3OP·0.5CH2Cl2 (422.71): С, 44.04; Н, 3.10; N,
9.94. Found: С, 43.75; Н, 3.01; N, 10.17.
4.7. Computational details
All the computations were performed with the Gaussian 09
package [30]. The equilibrium geometries were calculated using
B3LYP functional [31] and 6-311+G(d,p) basis set. Frequency
calculations at the same level of theory were also performed to
identify all the stationary points as minima (zero imaginary
frequencies). To estimate the effect of solvent medium (CHCl3, ε
= 4.8) on the energetics of obtained structures, the self-consistent
reaction field (SCRF) approach based on the polarized continuum
model (IPCM) [32] was used at the same level of theory to
calculate the single-point energy with solvent for the gas phase
stationary points.
o
[Cu(2-Py3P=O)I] (6). Garnet crystals, stable up to 200 C.
1
Yield: 41 mg (72%). Н NMR (400.13 MHz, CDCl3, ppm), δ:
5.52-5.56 (m, 3H, Py), 7.94-8.00 (m, 3H, Py), 8.38-8.42 (m, 3H,
Py), 9.05-9.06 (m, 3H, Py). 31Р NMR (161.98 MHz, CDCl3,
ppm), δ: –7.75. UV-Vis (CHCl3, λmax/nm): 257, 333, 430. Anal.
Calcd for C15H12CuIN3OP (471.70): С, 38.19; Н, 2.56; N, 2.56.
Found: С, 38.10; Н, 2.68; N, 2.41.
{Cu[(4-Me-2-Py)3P=O]I}·0.25C6H14 (7). Garnet crystals,
stable up to 200 oC. Yield: 43 mg (67%). 1Н NMR (400.13 MHz,
3
CDCl3, ppm), δ: 0.88-0.91 (t, JHH = 7.0 Hz, 6H, MeCH2), 1.24-
Acknowledgments
1.33 (m, 8H, CH2Me), 2.42 (s, 9H, MePy), 7.30 (d, 3JPH = 4.4 Hz,
3
4
This work was supported by the President of the Russian
Federation (program for the support of leading scientific schools,
grant NSh-156.2014.3).
3H, Py), 8.20 (d, JHH = 7.1 Hz, 3H, Py), 8.87 (d, JPH = 5.0 Hz,
3H, Py). 31Р NMR (161.98 MHz, CDCl3, ppm), δ: –6.64. Anal.
Calcd for C24H32CuIN3OP·0.25C6H14 (535.31): С, 43.75; Н,
4.05; N, 7.85. Found: С, 44.21; Н, 4.12; N, 7.64.
Appendix A. Supplementary material
[Cu(2-Py3P=S)I]·CH2Cl2 (8). Garnet crystals, stable up to 200
oC. Yield: 51 mg (75%). 1Н NMR (400.13 MHz, CDCl3, ppm), δ:
5.31 (s, 2H, CH2Cl2), 5.51-5.54 (m, 3H, Py), 7.94-7.97 (m, 3H,
CCDC 1010958-1010962 (5-9) 1019410 (10) contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge
3
4
Py), 8.76 (t, JHH = 8.0 Hz, 3H, Py), 9.07 (d, JPH = 4.5 Hz, 3H,
Py). 31Р NMR (161.98 MHz, CDCl3, ppm), δ: 11.82. UV-Vis
(CHCl3, λmax/nm): 260, 335, 444. Anal. Calcd for
C16H14Cl2CuIN3PS (572.70): С, 33.56; Н, 2.46; N, 7.34. Found:
С, 33.42; Н, 2.58; N, 7.21.
Crystallographic
Data
Centre
via
Appendix B. Supplementary data
o
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.jorganchem… .
[Cu(2-Py3P=Se)I]·0.6CH2Cl2 (9). Garnet crystals, > 165 C
1
dec. Yield: 49 mg (70%). Н NMR (400.13 MHz, CDCl3, ppm),
δ: 5.31 (s, 2H, CH2Cl2), 5.50-5.54 (m, 3H, Py), 7.94-7.99 (m, 3H,
3
4
Py), 8.91 (t, JHH = 8.5 Hz, 3H, Py), 9.06 (d, JPH = 4.8 Hz, 3H,
Py). 31Р NMR (161.98 MHz, CDCl3, ppm), δ: 10.29. UV-Vis
(CHCl3, λmax/nm): 259, 326, 444. Anal. Calcd for
C15H12CuIN3PSe·0.6CH2Cl2 (586.62): С, 31.99; Н, 2.27; N, 7.18.
Found: С, 31.71; Н, 2.12; N, 7.59.
References
[1] For reviews, see: (a) G.R. Newkome, Chem. Rev. 93
(1993) 2067; (b) Z.Z. Zhang, H. Cheng, Coord. Chem.
Rev. 147 (1996) 1; (c) P. Espinet, K. Soulantica, Coord.
Chem. Rev. 193-195 (1999) 499; (d) A.P. Sadimenko,
Adv. Heterocycl. Chem. 104 (2011) 391.
[2] (a) B.A. Trofimov, A.V. Artem’ev, S.F. Malysheva, N.K.
Gusarova, N.A. Belogorlova, A.O. Korocheva, Yu.V.
Gatilov, V.I. Mamatyuk, Tetrahedron Lett. 53 (2012)
2424; (b) B.A. Trofimov, N.K. Gusarova, A.V. Artem’ev,
S.F. Malysheva, N.A. Belogorlova, A.O. Korocheva, O.N.
Kazheva, G.G. Alexandrov, O.A. Dyachenko, Mendeleev
Commun. 22 (2012) 187; (c) S.F. Malysheva, A.O.
Korocheva, N.A. Belogorlova, A.V. Artem’ev, N.K.
Gusarova, B.A. Trofimov, Dokl. Chem. 445 (2012) 164.
[3] L.F. Szczepura, L.M. Witham, K.J. Takeuchi, Coord.
Chem. Rev. 174 (1998) 5.
[Cu(2-Py3P=O)(PPh3)]PF6·2CHCl3 (10). Yellowish crystals,
o
1
mp 134-136 C. Yield: 88 mg (89%). Н NMR (400.13 MHz,
CDCl3, ppm), δ: 7.49-7.59 (m, 18H, Ph, Py), 8.12-8.16 (m, 3H,
4
3
Py), 8.25 (d, JPH = 4.7 Hz, 3H, Py), 8.55 (t, JHH = 7.0 Hz, 3H,
Py). 31Р NMR (161.98 MHz, CDCl3, ppm), δ: –8.30 and –8.22 (s,
1
Py3P=O, Ph3P), –143.78 (quint, JPF = 716 Hz, PF6). Anal. Calcd
for C35H29Cl6CuF6N3OP3 (990.80): С, 42.43; Н, 2.95; N, 4.24.
Found: С, 42.30; Н, 2.71; N, 4.10.
[Cu(2-Py3P=O)(AsPh3)]PF6 (11). Yellowish powder, > 252
oC dec. Yield: 68 mg (85%). Н NMR (400.13 MHz, CDCl3,
1
ppm), δ: 7.47-7.58 (m, 18H, Ph, Py), 8.12-8.17 (m, 3H, Py), 8.35
(d, JPH = 4.5 Hz, 3H, Py), 8.54 (t, JHH = 7.2 Hz, 3H, Py). 31Р
NMR (161.98 MHz, CDCl3, ppm), δ: –8.82 (s, Py3P=O), –144.03
(quint, 1JPF = 712 Hz, PF6). Anal. Calcd for C33H27AsCuF6N3OP2
(795.99): С, 49.79; Н, 3.42; N, 5.28. Found: С, 49.50; Н, 3.25;
N, 5.50.
4
3
[4] From recent examples, see: (a) A. Bakhoda, N. Safari, V.
Amani, H.R. Khavasi, M. Gheidi, Polyhedron 30 (2011)
2950; (b) A.V. Artem’ev, N.K. Gusarova, S.F. Malysheva,
O.N. Kazheva, G.G. Alexandrov, O.A. Dyachenko, B.A.
Trofimov, Mendeleev Commun. 22 (2012) 294.
4.6. X-ray crystallography
Data were collected on a Bruker D8 Venture diffractometer
with MoKα (λ = 0.71073 Å) radiation using the φ and ω scans.
An empirical absorption correction was applied using the
SADABS program [28]. The structures were solved and refined
by direct methods using the SHELX [29]. All non-hydrogen
[5] For example, see: (a) K. Kurtev, D. Ribola, R.A. Jones,
D.J. Cole-Hamilton, G. Wilkinson, J. Chem. Soc., Dalton
Trans. (1980) 55; (b) A. Karam, R. Tenia, M. Martinez, F.
López-Linares, C. Albano, A. Diaz-Barrios, Y. Sánchez, E.
Catarí, E. Casas, S. Pekerar, A. Albornoz, J. Mol. Catal. A: