Activations of Silanes with [PhB(CH_2PPh_2)_3]Ir(H)(η^3-C_8H_(13)). Formation of Iridium Silylene Complexes via the Extrusion of Silylenes from Secondary Silanes R_2SiH_2
Abstract
The abstraction of methide from (Me_3P)_3Ir(SiHMes_2)(Me)(H) (1) with B(C_6F_5)_3 gave the silylene complex [fac-(Me_3P)_3(H)_2Ir(SiMes_2)][MeB(C_6F_5)_3] (2) via 1,2-hydrogen migration. Secondary silanes (H_2SiR_2) reacted with [PhBP_3]Ir(H)(η^3-C_8H^(13)) (3) (where [PhBP_3] = PhB(CH_2PPh_2)_3^-) to give silylene complexes of the type [PhBP_3](H)_2Ir═SiR_2 (R = 2,4,6-trimethylphenyl (Mes), 4a; R = Ph, 4b; R = Et, 4c; R = Me, 4d), with loss of cyclooctene. Analogously, the germylene complex [PhBP_3](H)2Ir═GeMes_2 was obtained via the reaction of 3 with Mes_2GeH_2. Primary silanes (H_3SiR) reacted with 3 to give [PhBP_3](H)_2Ir═Si(R)(c-C_8H_(15)) (R = Mes, 8a; R = 2,4,6-triisopropylphenyl (Trip), 8b) via an intermediate silylene complex with an Si−H bond, [PhBP_3](H)_2Ir═Si(R)(H). With tertiary silanes (R_3SiH), silyl-capped trihydride complexes of the type [PhBP_3]IrH_3(SiR_3) (R = Et, 7a; R = Me, 7b) and 1,3-cyclooctadiene were produced. The mechanisms of these processes are discussed.
Additional Information
© 2002 American Chemical Society. Received 13 May 2002. Published online 31 August 2002. Published in print 1 September 2002. Acknowledgment is made to the National Science Foundation for their generous support of this work. We than Dr. Fred Hollander of the UC Berkeley CHEXRAY facility for assistance with the X-ray structure determinations and for solving the structures for 4a and 8b.Attached Files
Supplemental Material - om020389u_s.pdf
Supplemental Material - om020389u_sa.pdf
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Additional details
- Eprint ID
- 79906
- DOI
- 10.1021/om020389u
- Resolver ID
- CaltechAUTHORS:20170808-080407504
- NSF
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2017-08-09Created from EPrint's datestamp field
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2021-11-15Created from EPrint's last_modified field