508
Can. J. Chem. Vol. 79, 2001
solution in vacuo. The residue was extracted with a 2:1 sol-
vent mixture of Et2O:CH2Cl2, and the extracts were filtered.
The solvent was again removed from the filtrate in vacuo,
and the residue was triturated with Et2O twice to obtain
CpMo(NO)(CH2Ph)Me (1) as an orange powder (0.110 g,
63% yield). Analytically pure samples of 1 were obtained by
extraction of the crude powder with a 1:1 solvent mixture of
THF:toluene, followed by chromatography using an Alu-
mina I column with toluene as eluant. The resulting orange
eluate was then reduced in volume in vacuo, hexanes were
added, and the solution was chilled to –30°C overnight to in-
duce the deposition of orange crystals.
CpMo(NO)(CH2Ph)Ph (2), CpMo(NO)(CH2Ph)(CϵCPh)
(3), and Cp2Mo(NO)(CH2Ph) (4) were synthesized from
CpMo(NO)(CH2Ph)(Cl) in an analogous manner, using
Ph2Mg·x(dioxane), LiCϵCPh, and Na(DME)Cp, respec-
tively, instead of Me2Mg·x(dioxane) as the hydrocarbylating
reagent.
non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were fixed in calculated positions with C—H = 0.98 Å.
Neutral atom scattering factors were taken from Cromer and
Waber (24). Anomalous dispersion effects were included in
Fcalc (25); the values for ∆f ′ and ∆f ′′ were those of Creagh
and McAuley (26). The values for the mass attenuation coef-
ficients are those of Creagh and Hubbell (27). All calcula-
tions were performed using the teXsan (28) crystallographic
software package of Molecular Structure Corp.
Acknowledgement
We are grateful to the Natural Sciences and Engineering
Research Council of Canada (NSERC) for support of this re-
search in the form of grants to P.L.
References
1. (a) E. Tran and P. Legzdins. J. Am. Chem. Soc. 119, 5071
(1997); (b) C.S. Adams, P. Legzdins, and E. Tran. J. Am.
Chem. Soc. 123, 612 (2001).
Synthesis of CpMo(NO)(CH2Ph)(OTf) (5)
First CH2Cl2 (20 mL) and then Et2O (20 mL) were added
via syringe to CpMo(NO)(CH2Ph)Cl (0.433 g, 1.36 mmol)
and AgOTf (0.350 g, 1.36 mmol). After ~10 min, a
flocculent white precipitate had formed in the orange solu-
tion. The mixture was filtered, and the Celite plug was
washed with Et2O (3 × 5 mL). The combined filtrates were
taken to dryness in vacuo, and the residue was triturated
twice with Et2O (10 mL) to obtain CpMo(NO)(CH2Ph)(OTf)
(5) as an orange powder (0.529 g, 83% yield).
2. P. Legzdins, S.J. Rettig, J.E. Veltheer, R.J. Batchelor, and
F.W.B. Einstein. Organometallics, 12, 3575 (1993).
3. P. Legzdins, J.E. Veltheer, M.A. Young, R.J. Batchelor, and
F.W.B. Einstein. Organometallics, 14, 407 (1995).
4. N.H. Dryden, P. Legzdins, S.J. Rettig, and J.E. Veltheer.
Organometallics, 11, 2583 (1992).
5. R. Poli and K.M. Smith. Organometallics, 19, 2850 (2000).
6. N.H. Dryden, P. Legzdins, J. Trotter, and V.C. Yee.
Organometallics, 10, 2857 (1991).
7. P. Legzdins, R.H. Jones, E.C. Phillips, V.C. Yee, J. Trotter, and
F.W.B. Einstein. Organometallics, 10, 986 (1991).
8. J. Ipaktschi, F. Mirzaei, G.J. Demuth-Eberle, J. Beck, and M.
Serafin. Organometalics, 16, 3965 (1997).
9. J.K. Hoyano, P. Legzdins, and J.T. Malito. J. Chem. Soc. Dal-
ton Trans. 1022 (1975).
Synthesis of [CpMo(NO)(CH2Ph)(L)][OTf] (L = PPh3
(6), NC5H5 (7))
Both triflate salts 6 and 7 may be obtained from either
isolated or in situ generated 5. The two-step synthesis of
[CpMo(NO)(CH2Ph)(PPh3)][OTf] from CpMo(NO)(CH2Ph)Cl
is described as a representative example.
First CH2Cl2 (10 mL) and then Et2O (10 mL) were added
to CpMo(NO)(CH2Ph)Cl (0.115 g, 0.36 mmol) and AgOTf
(0.092 g, 0.36 mmol). After ~10 min, the mixture was fil-
tered through Celite onto solid PPh3 (0.096 g, 0.36 mmol).
The solution was stirred briefly, and then hexanes (10 mL)
were added. The total volume of the solution was reduced to
~25 mL, and it was chilled to –30°C overnight to obtain
[CpMo(NO)(CH2Ph)(PPh3)][OTf] 6 as a yellow powder
(0.198 g, 79% yield).
10. (a) M.W. Hunt, W.G. Kita, B.E. Mann, and J.A. McCleverty. J.
Chem. Soc. Dalton Trans. 467 (1978); (b) M.W. Hunt, W.G.
Kita, and J.A. McCleverty. J. Chem. Soc. Dalton Trans. 474
(1978); (c) M.W. Hunt and J.A. McCleverty. J. Chem. Soc.
Dalton Trans. 480 (1978).
11. (a) R.B. King. Inorg. Chem. 7, 90 (1968); (b) F.A. Cotton and
P. Legzdins. J. Am. Chem. Soc. 90, 6232 (1968); (c) J.L.
Calderon, F.A. Cotton, and P. Legzdins. J. Am. Chem. Soc. 91,
2528 (1969); (d) F.A. Cotton and G.A. Rusholme. J. Am.
Chem. Soc. 94, 402 (1972); (e) J.W. Lauher and R. Hoffmann.
J. Am. Chem. Soc. 98, 1729 (1976); (f) E. de Jesús, A.
Vázquez de Miguel, P. Royo, A.M.M. Lanfredi, and A.
Tiripicchio. J. Chem. Soc. Dalton Trans. 2779 (1990).
12. G. Huttner, H.H. Brintzinger, L.G. Bell, P. Friedrich, V.
Bejenke, and D. Neugebauer. J. Organomet. Chem. 145, 329
(1978).
13. (a) M.J. Calhorda and L.F. Veiros. Coord. Chem. Rev. 185–
186, 37 (1999); (b) M.J. Calhorda, C.A. Gamelas, C.C.
Romão, and L.F. Veiros. Eur. J. Inorg. Chem. 331 (2000).
14. P. Legzdins and J.E. Veltheer. Acc. Chem. Res. 26, 41 (1993).
15. B. Alegre, E. de Jesús, A. Vázquez de Miguel, P. Royo,
A.M.M. Lanfredi, and A. Tiripicchio. J. Chem. Soc. Dalton
Trans. 819 (1988).
16. (a) J.D. Debad, P. Legzdins, S.J. Rettig, and J.E. Veltheer.
Organometallics, 12, 2714 (1993); (b) P. Legzdins and C.R.
Nurse. Inorg. Chem. 21, 3110 (1982); (c) T.T. Chin, P.
Legzdins, J. Trotter, and V.C. Yee. Organometallics, 11, 913
(1992); (d) P. Legzdins, S.J. Rettig, and S.F. Sayers. J. Am.
X-ray crystallographic analysis of Cp2Mo(NO)(CH2Ph)
(4)
A green/black plate of 4 having approximate dimensions
of 0.50 × 0.40 × 0.10 mm was mounted in a glass capillary.
All measurements were made on a Rigaku/ADSC CCD area
detector with graphite monochromated Mo Kα radiation.
Data were collected in 0.50° oscillations with 60.0 s expo-
sures. A sweep of data was done using φ oscillations from
0.0 to 190.0° at χ = –90° and a second sweep was performed
using ω oscillations between –23.0 and 18.0° at χ = –90°.
The crystal-to-detector distance was 39.20(3) mm. The de-
tector swing angle was –10°. The data were corrected for
Lorentz and polarization effects.
The structure was solved by heavy-atom Patterson meth-
ods (22) and expanded using Fourier techniques (23). The
© 2001 NRC Canada
Legzdins
