‡ Crystal data: for 1: C34H35Se3PW, M = 895.35, orthorhombic, space
group Pbca, a = 18.284(5), b = 20.171(7), c = 17.758(5) Å, V = 6549(2)
Å3, Z = 8, T = 293 K, m(Mo-Ka) = 69.37 cm–1, Rigaku-AFC7R, 6360
measured reflections (2qmax = 50°). The structure was solved by Patterson
methods and refined by full-matrix least squares. At convergence, R =
0.057, Rw = 0.058, and GOF = 1.44 for 352 variables refined against 4341
unique reflections [I > 1s(I)].
For 3: C29H51N3SeW, M = 704.55, monoclinic, space group P21/n, a =
9.7349(8), b = 18.9776(5), c = 17.4477(3) Å, b = 97.1791(7) °, V =
3198.1(2) Å3, Z = 4, T = 173 K, m(Mo-Ka) = 47.74 cm–1, Rigaku-AFC7
equipped with a MSC/ADSC Quantum1 CCD detector, 20472 measured
reflections (2qmax = 55°). The structure was solved by Patterson methods
and refined by full-matrix least squares (TEXSAN). At convergence, R =
0.077, Rw = 0.063, and GOF = 1.47 for 307 variables refined against all
7147 unique reflections.
crystallographic files in .cif format.
§ ButNC (1.0 mL, 8.8 mmol) was added to a mixture of Cp*WCl4 (0.46 g,
1.06 mmol) and LiSeBut (4.24 mmol) in THF (30 mL) at 278 °C. The
solution was warmed to room temperature and stirred for 0.5 h. The
resulting brown solution was evaporated to dryness. The residue was
crystallized from hexane to give 3 (0.31 g, 41%). 1H NMR (400 MHz,
C6D6), d 1.36 (s, 18H, But), 1.44 (s, 9H, But), 1.86 (s, 9H, But), 1.93 (s, 15H,
Cp*); IR n/cm21, 2038s, 1813s. Anal. calc.: C, 49.44; H, 7.30; N, 5.96.
Found: C, 49.07; H, 7.31; N, 5.61%.
Fig. 2 Molecular structure of 3. Selected bond lengths (Å) and angles (°):
W–Se 2.6271(7), W–C(15) 1.984(7), W–C(20) 2.039(7), W–C25 2.025(8),
Se–C(11) 2.019(8), N(1)–C(15) 1.220(9), N(2)–C(20) 1.148(9), N(3)–
C(25) 1.153(9); Se–W–C(5) 82.9(2), Se–W–C(15) 73.3(2), Se–W–C(20)
140.7(2), Se–W–C(25) 88.9(2), C(15)–W–C(20) 73.6(3), C(15)–W–C(25)
103.9(3), C(20)–W–C(25) 79.1(3).
the W(IV) thiolato complex Cp*W(SBut)3(CNBut) from the
Cp*WCl4/LiStBu reaction in the presence of ButNC.4 The
isolation of a W(II) selenolato complex, 3, is in accord with the
tendency of selenolato complexes to favor lower oxidation
states.
1 T. M. Trnka and G. Parkin, Polyhedron, 1997, 16, 1031; G. Parkin,
Prog. Inorg. Chem., 1998, 47, 1.
2 L. C. Roof and J. W. Kolis, Chem. Rev., 1993, 93, 1037; K. Tatsumi, H.
Kawaguchi and K. Tani, Angew. Chem., Int. Ed. Engl., 1993, 32, 591.
3 H. Kawaguchi and K. Tatsumi, J. Am. Chem. Soc., 1995, 117, 3885; H.
Kawaguchi, K. Yamada, J.-P. Lang and K. Tatsumi, J. Am. Chem. Soc.,
1997, 119, 10 346; K. Tatsumi, A. Tahara and A. Nakamura,
J. Organomet. Chem., 1994, 471, 111.
4 T. Nagasawa, H. Kawaguchi and K. Tatsumi, J. Organomet. Chem.,
1999, 592, 46.
5 S. C. O’Neal and J. W. Kolis, J. Am. Chem. Soc., 1988, 110, 1971.
6 A. Müller, E. Diemann, R. Jostes and H. Bögge, Angew. Chem., Int. Ed.
Engl., 1981, 20, 934.
7 R. W. M. Wardle, S. Bhaduri, C.-N. Chau and J. A. Ibers, Inorg. Chem.,
1988, 27, 1747; J. H. Shin and G. Parkin, Organometallics, 1995, 14,
1104.
8 C. E. Moore, Atomic Energy Levels, National Bureau of Standards,
Washington DC, 1949.
9 D. Rabinovich and G. Parkin, Inorg. Chem., 1995, 34, 6341; E. M.
Carnahan, R. L. Rardin, S. G. Bott and S. J. Lippard, Inorg. Chem.,
1992, 31, 5193; W. D. Jones, G. P. Foster and J. M. Putinas, Inorg.
Chem., 1987, 26, 2120; T. Adachi, N. Sasaki, T. Ueda, M. Kamikawa
and T. Yoshida, J. Chem. Soc., Chem. Commun., 1989, 1320; J. Chatt,
A. J. L. Pombeiro, R. L. Richards, G. H. D. Royston, K. W. Muir and R.
Walker, J. Chem. Soc., Chem. Commun., 1975, 708.
Notes and references
† All manipulations were carried out under an atmosphere of argon using
solvents purified by standard methods. A mixture of LiSeBut (7.60 mmol)
and Cp*WCl4 (0.86 g, 1.87 mmol) in THF (50 mL) was quickly added to a
slurry of Li2Se2 (1.40 mmol) in THF (20 mL) at 278 °C. The solution was
warmed up to room temperature and stirred for 2 h. After centrifugation, the
solution was evaporated to dryness. The residue was dissolved in MeCN (30
mL) to give a dark red solution and a brown solid. A solution of PPh4Br
(0.47 g, 1.12 mmol) in MeCN (20 mL) was added to the dark red
supernatant. Concentration and cooling to 220 °C afforded 0.38 g of 1 as
dark red crystals in 23% yield. The brown solid which was insoluble in
MeCN was recrystallized from toluene to provide 2 in 14% yield. Data for
1
1: H NMR (500 MHz, CDCl3), d 2.20 (s, 15H, Cp*), 7.6–8.0 (m, 20H,
PPh4). 77Se NMR (95.3 MHz, CDCl3, Me2Se), d 1437. IR n/cm–1: 284m
(WNSe). UV–VIS (MeCN): lmax/nm(e/M–1 cm–1) 299 (19000), 350 (sh),
437 (38000), 530 (sh). Anal. calc.: C, 45.61, H, 3.94. Found: C, 45.57; H,
1
3.98%. Data for 2: H NMR (500 MHz, CDCl3), d 2.27 (s, Cp*), 2.33 (s,
Cp*). IR n/cm21: 315m, 298m (WNSe). FAB-MS: 954 (M+). Anal. calc.: C,
10 W. Eikens, C. Kienitz, P. G. Jones and C. Thöne, J. Chem. Soc., Dalton
Trans., 1994, 3329.
25.18; H, 3.17. Found: C, 25.01; H, 3.30%.
1300
Chem. Commun., 2000, 1299–1300