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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

Feldman, Jay D. and Peters, Jonas C. and Tilley, T. Don (2002) 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. Organometallics, 21 (20). pp. 4065-4075. ISSN 0276-7333. doi:10.1021/om020389u. https://resolver.caltech.edu/CaltechAUTHORS:20170808-080407504

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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.


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http://dx.doi.org/10.1021/om020389uDOIArticle
http://pubs.acs.org/doi/full/10.1021/om020389uPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om020389uPublisherSupporting Information
ORCID:
AuthorORCID
Peters, Jonas C.0000-0002-6610-4414
Tilley, T. Don0000-0002-6671-9099
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.
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Issue or Number:20
DOI:10.1021/om020389u
Record Number:CaltechAUTHORS:20170808-080407504
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170808-080407504
Official Citation:Activations of Silanes with [PhB(CH2PPh2)3]Ir(H)(η3-C8H13). Formation of Iridium Silylene Complexes via the Extrusion of Silylenes from Secondary Silanes R2SiH2 Jay D. Feldman, Jonas C. Peters, and T. Don Tilley Organometallics 2002 21 (20), 4065-4075 DOI: 10.1021/om020389u
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79906
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:09 Aug 2017 20:39
Last Modified:15 Nov 2021 17:51

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