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Inorganic Syntheses. Volume 33 - Coucouvanis D.

Coucouvanis D. Inorganic Syntheses. Volume 33 - University of Michigan, 2002. - 299 p.
Download (direct link): inorganiksintesis2002.djvu
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and the coordinated pyridine is displaced.4
Procedure
An oven-dried, two-necked, 100-mL round-bottomed flask equipped with a
magnetic stirring bar, a reflux condenser, a T-shaped N2 inlet, and a
septum in a glovebox is charged with a mixture of [ (?/5 - 5 H4 Me) Ti
1 (NP h) ]215 (1.50 g,
I.96 mmol) and Me3SnF (1.08 g, 5.92 mmol). Toluene (50 ml.1 and pyridine
(0.5 mL) are added via a syringe. The mixture is stirred for 8 h at 60
C. All volatile contents are removed carefully under vacuum, yielding an
orange solid. The solid is washed once with cold hexane (20 mL).
Recrystallization from toluene (20 mL) at - 24 C affords [(775-
C5H4Me)TiF(NPh)]2 as yellow-orange crystals that are filtered off and
dried in vacuo, yield 1.26 g (90%).
Characterization Data. Melting point: 153 C. !H NMR data: 6 7.10-6.79
(m, 5H, NPh), 6.14 (t, / = 2.7 Hz, 2H, C5H4Me), 5.65 (t, / = 2.7 Hz,
2H,
238
Compounds of General Interest
CsH4Me), 1.96 (s, 3H, CsR^Me) ppm. 19F NMR: 6 95.9(s) ppm. Mass spectrum
(m/z): 474 (M, 60%), 395 (M-Csft^e, 100%).
Elemental Analysis Data. Calcd. for C^H^F^^^ (474.22): , 60.79%;
H, 5.10%; F, 8.01%; N, 5.91%. Found: C, 60.7%; H, 5.0%; F, 8.0%; N, 5.9%.
F. BISPENTAMETHYLCYCLOPENTADIENYL(TITANIUM FLUORIDE) (*/5-C5Me5)2TiF
Procedure
A 100-mL, two-necked, round-bottomed flask is fitted with a magnetical
stirrer, a nitrogen gas inlet tube, and a dropping funnel. The flask is
charged with Me3SnF (0.55 g, 3.0 mmol) in a drybox. Toluene (30 mL) is
added via a syringe. A solution of (775-C5Me5)2TiCl (0.06 g, 3.0 mmol) in
toluene (30 mL) is added dropwise under stirring. The solid disappears
after stirring for 3 h at room temperature. The solvent is removed in
vacuo and the residue sublimed at 94C/10-2 mbar to give 0.88 g (88%) of
(775-C5Me5)2TiF as a green solid.
Characterization Data. Melting point: 184 C. IR (KBr): v 1261(m),
1022(s), 562(s), 445(s) cm-1. Mass spectrum (m/z): 337 (M, 65%), 135
(C5Me5, 100%).
Elemental Analysis Data. Calcd. for C2oH3oFTi (337.34): C, 71.21%; H,
8.96%;
F, 5.62%. Found: C, 71.0%; H, 8.9%; F, 5.8%.
References and Notes
1. A. Herzog, F.-Q. Liu, H. W. Roesky, A. Demar, K. Keller, M.
Noltemeyer, and F. Pauer, Organometallics 13, 1251 (1994).
2. H. W. Roesky, A. Herzog, and F.-Q. Liu, J. Fluorine Chem. 71, 161
(1995).
3. H. W. Roesky, A. Herzog, and F.-Q. Liu, J. Fluorine Chem. 72, 183
(1995).
4. F.-Q. Liu, A. Herzog, H. W. Roesky, and I. Uson, Inorg. Chem. 35,
741 (1996).
5. E. F. Murphy, T. Ltibben, A. Herzog, H. W. Roesky, A. Demar, M.
Noltemeyer, andH.-G. Schmidt, Inorg. Chem. 35, 23 (1996).
6. E. F. Murphy, P. Yu, S. Dietrich, H. W. Roesky, E. Parisini, and M.
Noltemeyer, J. Chem. Soc., Dalton Trans., 1983 (1996).
7. S. A. A. Shah, H. Dom, A. Voigt, H. W. Roesky, E. Parisini, H.-G.
Schmidt, andM. Noltemeyer, Organometallics 15, 3176 (1996).
8. M. G. Walawalkar, R. Murugavel, and H. W. Roesky, Eur. J. Solid
State Inorg. Chem. 33, 943
(1996).
9. (a) E. Krause, Ber. Dtsch. Chem Ges. 51, 1447 (1918); (b) W. K.
Johnson, J. Org. Chem. 25, 2253 (1960); (c) L. E. Levchuk, J. R. Sams,
and F. Aubke, Inorg. Chem. 11, 43 (1972).
10. A. M. Cardoso, R. J. H. Clark, and S. Moorhouse, J. Chem. Soc.,
Dalton Trans., 1156 (1980).
41. Seven-Coordinate [MI2(CO)3(NCMe)2], [MI2(CO)3(NCMe)(PPh3)J 239
11. P. T. Wolczanski and J. E. Bercaw, Organometallics 1, 793 (1982).
12. D. M. Roddick, M. D. Fryzuk, P. F. Seidler, G. L. Hillliouse, and J.
E. Bercaw, Organometallics
4, 97 (1985).
13. H. W. Roesky, I. Leichtweis, and M. Noltemeyer, Inorg. Chem. 32,
5102 (1993).
14. F. Palacios, P. Royo, R. Serrano, J. L. Balcazar, I. Fonseca, and F.
Florencino, J. Organomet. Chem. 375, 51 (1989).
15. [(r/5-C5H^Me)TiCl(NPhI]2 is prepared according to the methods in Y.
Bai, H. W. Roesky,
H.-G. Schmidt, and M. Noltemeyer, Z. Naturforsch. 47B, 603 (1992).
16. J. W. Pattiasina, H. J. Heeres, F. van Bolhuis, A. Meetsma, J. H.
Teuben, and A. L. Spek, Organometallics 6, 1004 (1987).
41. SEVEN-COORDINATE [MI2(CO)3(NCMe)2], [MI2(CO)3 (NCMe)(PPh3)], AND
ALKYNE [MI2(CO)(NCMe)(i/2-RC2R)2] COMPLEXES OF MOLYBDENUM(II) AND
TUNGSTEN(II)
Submitted by PAUL K. BAKER* and MARGARET M. MEEHAN Checked by HAIDOO
KWEN, AMY ABBOTT, and ERIC A. MAATTA1
The importance of seven-coordinate halocarbonyl complexes has been
highlighted by their applications as homogeneous catalysts. For example,
Bencze and Kraut-Vass1 have shown that the complexes [MX2(CO)3L2] (M =
Mo,W; X = Cl,Br; L = PPh3,AsPh3) are active single-component catalysts
for the ring-opening polymerization of norbomene and norbornadiene. The
polymerization mechanism involves initial displacement of L by the
alkene, followed by a
1,2-hydrogen shift to give a carbene intermediate.2 In 1966, Colton and
Tomkins3 described the synthesis of the highly reactive and relatively
unstable, chloro-bridged dimer {[Mo(/i-Cl)Cl(CO)4]2|. They followed this
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