A. Beleaga et al. / Journal of Organometallic Chemistry 694 (2009) 1308–1316
1315
6.2 Hz], 2.31s (3H, N–CH3), 2.53, 2.61br [8H, H8,9,10,11], 3.61s (2H,
epoxy glue on cryoloops, and the data were collected at room tem-
perature (297 K). The structures were refined with anisotropic
thermal parameters. The hydrogen atoms were refined with a rid-
ing model and a mutual isotropic thermal parameter. The isopro-
poxy groups of compound 4 are disordered over two positions
and the atoms have been refined with a site occupancy of 57:43
(A/B). The Flack parameter for compound 6 is 0.038(18). In both
cases, the C–C bonds were restrained to 1.54 Å. The software pack-
age SHELX-97 was used for structure solving and refinement [46].
The drawings were created with the program DIAMOND [47].
3
3
H7), 4.78dh [2H, P–O–CH(CH3)2, JPH 12.2, JHH 6.1 Hz], 7.10 m
3
(2H, H3,4), 7.21 m (1H, H5), 7.98d (1H, H6, JHH 7.9 Hz). 13C NMR:
3
d
23.36d [CA, P–O–CH(CH3)2, JPC 5.7 Hz], 23.67d [CB, P–O–
3
CH(CH3)2, JPC 4.2 Hz], 45.83 (N–CH3), 51.88 (C8,11), 54.40 (C9,10),
2
62.69 (C7), 73.02d [P–O–CH(CH3)2, JPC 6.9 Hz], 125.96 (C4),
127.26 (C3), 128.14 (C5), 130.51 (C6), 134.63 (C2), 137.73 (C1). 31P
NMR: d 88.2. 77Se NMR: d 585.1. IR (cmꢂ1):
mas(PS2) 642vs, ms(PS2)
552s.
4.6. Preparation of [C,N-2-(N-morpholinylmethyl)phenyl]-
selenium(II)diphenyldithiophosphinate, [2-{O(CH2CH2)2NCH2}-
Acknowledgements
C6H4]SeSP(S)Ph2 (5)
This work was supported by the Romanian Ministry of Educa-
tion and Research (Grants CEx 11-55/2006 and CEx D11-16/2005).
Stoichiometric amounts of [2-{O(CH2CH2)2NCH2}C6H4]SeCl
(0.113 g, 0.39 mmol) and Ph2P(S)SNH4 (0.104 g, 0.39 mmol) were
stirred in CH2Cl2 (50 ml) for 12 h, at room temperature. The solu-
tion was concentrated in vacuum to minimum volume and then
kept at low temperature (ꢂ20°) for 24 h, when the title compound
deposited as a pale yellow solid. The compound was filtered off and
recrystallized from CH2Cl2/n-hexane (1:5, v/v). Yield: 0.17 g (85%).
M.p. 179 °C. Anal. Calc. for C23H24NOPS2Se: C, 54.76; H, 4.79; N,
2.78. Found: C, 54.48; H, 4.54; N, 2.62%. 1H NMR: d 2.42br (4H,
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
References
H8,11), 3.38s (2H, H7), 3.55t (4H, H9,10
,
3JHH 4.2 Hz), 6.95d (1H, H3,
[1] G. Mugesh, H.B. Singh, Chem. Soc. Rev. 29 (2000) 347.
[2] G. Mugesh, H.B. Singh, Acc. Chem. Res. 35 (2002) 226.
[3] K. Kandasamy, S. Kumar, H.B. Singh, R.J. Butcher, K.T. Holman, Eur. J. Inorg.
Chem. (2004) 1014.
[4] S. Kumar, K. Kandasamy, H.B. Singh, G. Wolmershauser, R.J. Butcher,
Organometallics 23 (2004) 4199.
[5] T.M. Klapötke, B. Krumm, K. Polborn, J. Am. Chem. Soc. 126 (2004) 710.
[6] M. Kulcsar, A. Silvestru, C. Silvestru, J.E. Drake, C.L.B. Macdonald, M.E.
Hursthouse, M.E. Light, J. Organometal. Chem. 690 (2005) 3217. and
references therein.
[7] Y. You, K. Ahsan, M.R. Detty, J. Am. Chem. Soc. 125 (2003) 4918.
[8] A. Panda, G. Mugesh, H.B. Singh, R.J. Butcher, Organometallics 18 (1999)
1986.
3JHH 7.0 Hz), 7.04 m (2H, H4,5), 7.33 m (6H, P–C6H5-meta + para),
3
3
7.82d (1H, H6, JHH 7.5 Hz), 7.92dd (4H, P–C6H5-ortho, JPH 13.9,
3JHH 7.0 Hz). 13C NMR: d 51.93 (C8,11), 62.66 (C7), 66.07 (C9,10),
3
125.86 (C4), 127.07 (C3), 127.82d (P–C6H5-meta, JPC 13.2 Hz),
127.92 (C5), 130.36 (C6), 131.15 (P–C6H5-para, JPC 2.8 Hz),
4
2
131.33d (P–C6H5-ortho, JPC 10.8 Hz), 133.91 (C1), 134.71d (P–
C6H5-ipso, JPC 82.9 Hz), 137.19 (C2). 31P NMR:
d
65.3 (1JPC
1
82.6 Hz). 77Se NMR: d 552.1.
[9] T. Wirth, Angew. Chem., Int. Ed. 39 (2000) 3740.
4.7. Preparation of [C,N-2-(N-morpholinylmethyl)phenyl]-
[10] T. Wirth (Ed.), Organoselenium Chemistry: Modern Developments in Organic
Synthesis, Topics in Current Chemistry, vol. 208, Springer, Berlin, 2000.
[11] K. Fujita, K. Murata, M. Iwaoka, S. Tomoda, Tetrahedron 53 (1997) 2029.
[12] C. Santi, T. Wirth, Tetrahedron: Asymmetry 10 (1999) 1019.
[13] K. Hiroi, Y. Suzuki, I. Abe, Tetrahedron: Asymmetry 10 (1999) 1173.
[14] M. Tiecco, L. Testaferri, C. Santi, C. Tomassini, F. Marini, L. Bagnoli, A.
Temperini, Tetrahedron: Asymmetry 11 (2000) 4645.
[15] M. Uchiyama, S. Satoh, A. Ohta, Tetrahedron Lett. 42 (2001) 1559.
[16] M. Uchiyama, M. Hirai, M. Nagata, R. Katoh, R. Ogawa, A. Ohta, Tetrahedron
Lett. 42 (2001) 4653.
[17] M. Tiecco, L. Testaferri, C. Santi, C. Tomassini, F. Marini, L. Bagnoli, A.
Temperini, Angew. Chem., Int. Ed. 42 (2003) 3131.
[18] M. Iwaoka, S. Tomoda, J. Am. Chem. Soc. 116 (1994) 2557.
[19] G. Mugesh, W.-W. du Mont, H. Sies, Chem. Rev. 101 (2001) 2125. and
references therein.
[20] G. Mugesh, A. Panda, H.B. Singh, N.S. Punekar, R.J. Butcher, J. Am. Chem. Soc.
123 (2001) 839.
[21] M.L. Jauslin, T. Wirth, T. Meier, F. Schoumacher, Hum. Mol. Genet. 11 (2002)
3055.
[22] J.E. Drake, M.B. Hursthouse, M. Kulcsar, M.E. Light, A. Silvestru, J. Organometal.
Chem. 623 (2001) 153.
[23] C. Deleanu, J.E. Drake, M.B. Hursthouse, M. Kulcsar, M.E. Light, A. Silvestru,
Appl. Organomet. Chem. 16 (2002) 727.
selenium(II)diisopropyldithiophosphate, [2-{O(CH2CH2)2NCH2}-
C6H4]SeSP(S)(OPri)2 (6)
Stoichiometric amounts of [2-{O(CH2CH2)2NCH2}C6H4]2Se2
(0.27 g, 0.53 mmol) and [(PriO)2P(S)S]2 (0.23 g, 0.53 mmol) were
stirred in CH2Cl2 (30 ml) for 12 h, at room temperature. The yellow
solution was concentrated in vacuum to minimum volume and
then kept at low temperature (ꢂ20 °C) for 24 h, when the title
compound deposited as a yellow solid. The compound was filtered
off and recrystallization from CH2Cl2/n-hexane (1:5, v/v) affords
isolation of the title compound as yellow crystals. Yield: 0.32 g
(63%). M.p. 137–138 °C. Anal. Calc. for C17H28NO3PS2Se: C, 43.59;
H, 6.02; N, 2.99. Found: C, 43.24; H, 5.83; N, 2.62%. 1H NMR: d
1.19d [6HA, P–O–CH(CH3)2, 3JHH 6.0 Hz], 1.28d [6HB, P–O–CH(CH3)2,
3JHH 6.0 Hz], 2.56br (4H, H8,11), 3.61s (2H, H7), 3.75t (4H, H9,10, 3JHH
3
3
4.2 Hz), 4.78dh [2H, P–O–CH(CH3)2, JPH 12.0, JHH 6.0 Hz], 7.12m
(2H, H3,4), 7.23 m (1H, H5), 7.99d (1H, H6, JHH 7.9 Hz). 13C NMR:
23.29d [CA, P–O–CH(CH3)2, JPC 5.6 Hz], 23.63d [CB, P–O–
CH(CH3)2, JPC 4.0 Hz], 52.28 (C8,11), 63.11 (C7), 66.48 (C9,10),
3
3
d
[24] M. Kulcsar, A. Beleaga, C. Silvestru, A. Nicolescu, C. Deleanu, C. Todasca, A.
Silvestru, Dalton Trans. (2007) 2187.
3
[25] I. Haiduc, R.B. King, M.G. Newton, Chem. Rev. 94 (1994) 301.
[26] M.G. Newton, R.B. King, I. Haiduc, A. Silvestru, Inorg. Chem. 32 (1993) 3795.
[27] A. Silvestru, I. Haiduc, K.H. Ebert, H.J. Breunig, Inorg. Chem. 33 (1994) 1253.
[28] A. Silvestru, I. Haiduc, K.H. Ebert, H.J. Breunig, D.B. Sowerby, J. Organomet.
Chem. 482 (1994) 253.
2
73.16d [P–O–CH(CH3)2, JPC 6.8 Hz], 126.07, 127.52 (C3,4), 128.26
(C5), 130.60 (C6), 134.56 (C1), 137.40 (C2). 31P NMR: d 87.7. 77Se
NMR: d 573.9. IR (cmꢂ1):
m
as(PS2) 644vs,
ms(PS2) 553s.
[29] A. Silvestru, I. Haiduc, H.J. Breunig, K.H. Ebert, Polyhedron 14 (1995) 1175.
[30] A. Silvestru, R.A. Toscano, I. Haiduc, H.J. Breunig, Polyhedron 14 (1995) 2047.
[31] W. McFarlane, R.J. Wood, J. Chem. Soc. A (1972) 1397.
[32] J. Emsley, Die Elemente, Walter de Gruyter, Berlin, 1994.
[33] B. Krebs, G. Henkel, Z. Anorg. Allg. Chem. 475 (1981) 143.
[34] L.M. Opris, A. Silvestru, C. Silvestru, H.J. Breunig, E. Lork, Dalton Trans. (2003)
4367.
[35] O. Bumbu, C. Silvestru, M.C. Gimeno, A. Laguna, J. Organomet. Chem. 689
(2004) 1172.
[36] L.M. Opris, A. Silvestru, C. Silvestru, H.J. Breunig, E. Lork, Dalton Trans. (2004)
3575.
4.8. X-ray structure determination
The details of crystal structure determination and refinement
for compounds PhSeSP(S)Ph2 (1), [2-{MeN(CH2CH2)2NCH2}C6H4]-
SeSP(S)Ph2 (3), [2-{MeN(CH2CH2)2NCH2}C6H4]SeSP(S)(OPri)2 (4)
and [2-{O(CH2CH2)2NCH2}C6H4]SeSP(S)(OPri)2 (6) are given in Ta-
ble 3. Data were collected with a Bruker SMART APEX diffractom-
eter by using graphite-monochromated Mo-K
(k = 0.71073 Å). For this purpose, block crystals were attached with
a
radiation
[37] R.A. Varga, C. Silvestru, C. Deleanu, Appl. Organomet. Chem. 19 (2005) 153.