Abstract
The reducing agent [Et3BH][Li] reacts with diag-CpRe(CO)2Br2 in THF at −78∘C by polyene ring attack to give the anionic rhenium(I) compound [(η4-C5H6)Re(CO)2Br2]−. Monitoring the reaction by low-temperature IR spectroscopy has revealed that the reaction between diag-CpRe(CO)2Br2 and hydride is instantaneous and that the known compounds CpRe(CO)2Br− and CpRe(CO)2Br(H) are not formed as the principal reduction products. The reduced compound [(η4-C5H6)Re(CO)2Br2]− is extremely temperature sensitive and decomposes upon warming to afford low yields of CpRe(CO)3. We have explored the reactivity of the hydride reduction product with added CO and have isolated and structurally characterized the anionic tetracarbonyl compound trans(Br)-[Re(CO)4Br2]− as the tetraphenylphosphonium salt. trans(Br)-[Re(CO)4Br2][PPh4] crystallizes in the monoclinic space group C2/c, a = 16.908(2) Å, b = 7.1579(7) Å, c = 23.543(2) Å, β = 96.144(9)∘, V = 2832.9(5) Å3, Z = 4, D cacl = 1.870 g/cm3; R = 0.0419, R w = 0.0450 for 1629 observed reflections with I > 3σ(I). The reaction between the product of hydride reduction and dppe is shown by IR and 31P NMR spectroscopies to produce mer-cis-BrRe(CO)2(η2-dppe)(η1-dppe).
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References
(a) King, R.B.; Reimann, R.H.; Darensbourg, D.J. J. Organomet. Chem. 1975, 93, C23.
(b) King, R.B.; Reimann, R.H. Inorg. Chem. 1976, 15, 179.
(a) Yang, G.K.; Bergman, R.G. Organometallics 1985, 4, 129.
(b) Lindner, E.; Wassing, W. Organometallics 1991, 10, 1640.
(c) Moss, J.R.; Graham, W.A.G. Inorg. Chem. 1977, 16, 75.
Hoyano, J.K.; Graham, W.A.G. Organometallics 1982, 1, 783.
For a few representative examples, see: (a) Janowicz, A.H.; Bergman, R.G. J. Am. Chem. Soc. 1983, 105, 3929.
(b) Buchanan, J.M.; Stryker, J.M.; Bergman, R.G. J. Am. Chem. Soc. 1986, 108, 1537.
(c) Stoutland, P.O.; Bergman, R.G. J. Am. Chem. Soc. 1988, 110, 5732.
(d) Jones, W.D.; Feher, F.J. J. Am. Chem. Soc. 1984, 106, 1650; 1985, 107, 620.
(e) Jones, W.D.; Feher, F.J. Acc. Chem. Res. 1989, 22, 91.
(a) Lee, S.W.; Yang, K.; Martin, J.A.; Bott, S.G.; Richmond, M.G. Inorg. Chim. Acta 1995, 232, 57.
(b) Lee, S.W.; Richmond, M.G. Kor. Bull. Chem. 1994, 15, 1013.
(c) See also: Nunn, C.M.; Cowley, A.H.; Lee, S.W.; Richmond, M.G. Inorg. Chem. 1990, 29, 2105.
Luetkens, M.L.; Sattelberger, A.P.; Murray, H.H.; Basil, J.D.; Fackler, J.P., Jr. Inorg. Synth. 1989, 26, 7.
Shriver, D.F. The Manipulation of Air-Sensitive Compounds; McGraw-Hill: New York, 1969.
For two reports for the facile loss of an η4-cyclopentadiene ring from related rhenium compounds, see: Jones, W.D.; Maguire, J.A. Organometallics 1987, 6, 1301, 1728.
Cotton, F.A.; Kraihanzel, C.S. J. Am. Chem. Soc. 1962, 84, 4432.
Cotton, F.A.; Wilkinson, G. Advanced Inorganic Chemistry, 3rd ed., Wiley-Interscience: New York, 1972.
Carriedo, G.A.; Rodríguez, M.L.; Gracía-Granda, S.; Aguirre, A. Inorg. Chim. Acta 1990, 178, 101.
For spectroscopic data on related mer,cis-BrRe2P3 compounds, see: (a) Fernández-García, F.; Bolaño, S.; Carballo, R.; García-Fontán, S.; Bravo, J. Polyhedron 2001, 20, 2675. (b) Carballo, R.; Losada-González, P.; Vázquez-López, E.M. Z. Anorg. Allg. Chem. 2003, 629, 249.
Sang, W.L. Dissertation; University of North Texas, 1989.
F.W.B. Einstein A.H. Klahn-Oliva D. Sutton K.G. Tyers (1986) Organometallics 5 53 Occurrence Handle10.1021/om00132a009 Occurrence Handle1:CAS:528:DyaL28XovVOmtw%3D%3D
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Bott, S.G., Lee, SW., Yang, K. et al. Polyene ring attack in diag-CpRe(CO)2Br2 by hydride and cyclopentadiene displacement to furnish trans(Br)-[Re(CO)4Br2]− under CO: X-ray diffraction structure of trans(Br)-[Re(CO)4Br2][PPh4]. J Chem Crystallogr 35, 203–209 (2005). https://doi.org/10.1007/s10870-005-2958-1
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DOI: https://doi.org/10.1007/s10870-005-2958-1