K.-H. Yih et al. / Inorganic Chemistry Communications 6 (2003) 213–216
215
Scheme 2.
a doubly-bridging bidentate ligand has not been
Acknowledgements
reported in the literature, although Group VB [11],
Group VIIB [12] and Group VIIIB [13] metal complexes
with pyS ligands are known.
We thank the National Science Council of Taiwan,
the Republic of China for support.
Although the dinuclear compound 1a is apparently
strongly held by sulfur bridges and is thermally stable,
these bridges are easily cleaved by addition of r donor
ligands. Thus treatment of 1a with C5H10NHat ambient
References
temperature yields
a
mononuclear complex ½Mo
[1] S.P. Cramer, K.O. Hodgson, W.O. Gillum, L.E. Mortenson, J.
Am. Chem. Soc. 100 (1978) 3398.
ðg3-C3H5Þðg2-pySÞðC5H10NHÞðCOÞ2 (2) in good yield
(Scheme 1) in which the pyS ligand acts as a chelating
three-electron (counted as a radical) ligand. The yellow
compound 2 is slightly air-sensitive, soluble in polar
solvent, and slightly soluble in n-hexane. The FAB mass
spectrum of 2 shows a parent peak corresponding to the
[Mþ] molecular mass. Similar spectroscopic phenomena
[2] K. Anzenhofer, J.J. de Boer, Acta Cryst. B 25 (1969) 1419.
[3] (a) M.R. Houchin, K. Mitsios, Inorg. Chim. Acta 65 (1982) L147;
(b) K.B. Shiu, K.H. Yih, S.L. Wang, F.L. Liao, J. Organomet.
Chem. 420 (1991) 359.
[4] (a) F.A. Cotton, A.G. Stanislowski, J. Am. Chem. Soc. 96 (1974)
5074;
(b) S.F. Lush, S.H. Wang, G.H. Lee, S.M. Peng, S.L. Wang, R.S.
Liu, Organometallics 9 (1990) 1862.
1
of the carbonyl group and allyl moiety in IR, H, and
1
[5] K.H. Yih, G.H. Lee, Y. Wang, J. Organomet. Chem. 588 (1999)
125.
13Cf Hg NMR spectra [7] lead us to believe that com-
plex 2 contains the similar intramolecular trigonal twist
rotational behavior as those of the 18 electron dithio-
phosphate complexes ½Moðg3-C3H5Þfg3-S2PðOEt2Þg
ðCH3CNÞðCOÞ2 [5], ½Moðg3-C3H5Þfg3-S2PðOEt2ÞgðC5
H10NHÞðCOÞ2 [5] and the dithiocarbonate complex
½Moðg3-C3H5Þðg2-S2COEt2ÞðCH3CNÞðCOÞ2 [6]. Treat-
ment of 2 with CS2 no 16 electron dithiocarbamate
complex ½Moðg3-C3H5Þðg2-S2CNC5H10ÞðCOÞ2 can
be obtained. Complexes 1 and 2 can be prepared
bythe reactions of ½Moðg3-C3H5Þfg3-S2PðOEt2ÞgðCH3
CNÞðCOÞ2, ½Moðg3-C3H5Þfg3-S2PðOEt2ÞgðC5 H10NHÞ
ðCOÞ2 and pySHwith releasing of the ðEtOÞ2P(S)SH
ligand, respectively (Scheme 2). Attempt to synthesis a
bisalkyne product as that of complex ½MoðPhCBCPhÞ2
fg2-S2PðOEt2Þg2 [14] from the reaction of 1a with
diphenylacetylene, no reaction occurred even in reflux-
ing acetonitrile for 1 h. From the mention of above, one
can conclude that the pySHligand is a stronger p-ac-
cepter ligand than the ðEtOÞ2P(S)SHligand. Currently,
the reactions of 1a with nitrogen, sulfur and phosphorus
ligands are under investigation.
[6] K.H. Yih, G.H. Lee, Y. Wang, Hungkuang Journal 40 (2002) 1.
[7] Spectroscopy for 1a: IR (KBr, cmꢀ1) t(CO) 1937(vs), 1922(vs),
1875(vs), 1858(vs). 1HNMR (500 MHz, DMSO- d6, 298 K): d
1.00, 1.33 (d, JH–H ¼ 9:6 Hz, 2H, Hanti of allyl), 3.06, 3.43 (br, 2H,
Hsyn of allyl), 3.83 (m, 1H, CH of allyl), 6.77 (d, JH–H ¼ 8:1 H z,
1H, SCCH), 6.83 (t, JH–H ¼ 6:3 Hz, 1H, NCHCH), 7.39 (t,
JH–H ¼ 7:7 Hz, 1H, SCCHCH), 7.88 (d, JH–H ¼ 4:6 Hz, 1H,
1
NCH). 13Cf Hg NMR (75 MHz, DMSO-d6, 298 K): d 51.9, 62.9
(s, C@CH2), 74.6 (s, C@CH2), 117.3 (s, 5-C of pyS), 126.2 (s, 3-C
of pyS), 136.9 (s, 4-C of pyS), 146.2 (s, 6-C of pyS), 176.7 (s, 2-C of
pyS), 228.9, 231.2 (s, CO). mp 195 °C dec. Anal. Calcd. for
C
20H18N2O4S2Mo2: C, 39.61; H, 2.99; N, 4.62%. Found: C, 39.80;
H, 2.60; N, 4.50. Spectroscopy for 1b: IR (KBr, cmꢀ1) t(CO)
1933(vs), 1915(vs), 1870(vs), 1849(vs). 1HNMR (500 MHz,
DMSO-d6, 298 K): d 1.53 (d, JH–H ¼ 6:4 Hz, 2H, Hanti of allyl),
2.49 (br, 2H, Hanti of allyl), 3.45 (br, 2H, Hsyn of allyl), 3.92 (s,
6H, CH3syn of allyl), 4.34 (s, 2H, Hc of allyl), 7.40 (d, JH–H ¼ 8:0
Hz, 2H, SCCH), 7.46 (t, JH–H ¼ 6:2 Hz, 2H, NCHCH), 8.00 (br,
1
2H, SCCHCH), 8.56 (br, 2H, NCH). 13Cf Hg NMR (125 MHz,
CDCl3, 298 K): d 18.2 (s, CH3), 45.8, 62.9 (s, C@CH2), 78.5 (s,
C@CH2), 120.7 (s, 5-C of pyS), 129.1 (s, 3-C of pyS), 134.8 (s, 4-C
of pyS), 148.3 (s, 6-C of pyS), 178.7 (s, 2-C of pyS), 225.9, 230.2 (s,
CO). mp 205 °C dec. Anal. Calcd. for C22H22N2O4S2Mo2:C,
41.65; H, 3.50; N, 4.42%. Found: C, 41.82; H, 3.46; N, 4.31.
1
Spectroscopy for 2: IR (KBr, cmꢀ1) t(CO) 1924(vs), 1838(vs). H