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Structural and Chemical Properties of Zwitterionic Iridium Complexes Featuring the Tripodal Phosphine Ligand [PhB(CH_2PPh_2)_3]^-

Feldman, Jay D. and Peters, Jonas C. and Tilley, T. Don (2002) Structural and Chemical Properties of Zwitterionic Iridium Complexes Featuring the Tripodal Phosphine Ligand [PhB(CH_2PPh_2)_3]^-. Organometallics, 21 (20). pp. 4050-4064. ISSN 0276-7333. doi:10.1021/om0205086. https://resolver.caltech.edu/CaltechAUTHORS:20170309-101305346

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Abstract

Several new iridium compounds bearing the PhB(CH_2PPh_2)_3^- (herein abbreviated as [PhBP_3]) ligand have been prepared and characterized, and a comparison of steric, electronic, and chemical properties is made with those of related pentamethylcyclopentadienyl (Cp^*) and hydridotris(3,5-dimethylpyrazolyl)borate (Tp^(Me)_2) complexes. The complexes [PhBP_3]Ir(H)(η_3-C_8H_(13)) (2) and [PhBP_3]Ir(H)(η^3-C_3H_5) (3) were synthesized from the reaction of [Li(TMED)][PhBP_3] (1) with the corresponding [(alkene)_2IrCl]_2 complex. These allyl complexes serve as precursors to the dihalides [PhBP_3]IrX_2 (10, X = I; 12, X = Cl). In addition to these dihalides, the five-coordinate species [PhBP_3]IrMe_2 (16) and [ClB(CH_2PPh_2)_3]IrCl_2 (13) have been isolated. Addition of CO to 2 or 3 gave [PhBP_3]Ir(CO)_2 (7), while reaction of H_2 with 2 yielded {[PhBP_3]IrH_2}_2 (8) in benzene and [PhBP_3]Ir(COE)H_2 (9) in THF (where COE = cyclooctene). Complex 2 reacted with PMePh_2 to give [PhBP_3]Ir(PMePh_2)H_2 (5) and 1,3-cyclooctadiene. The protonation of 5 with [H(OEt_2)]{B[3,5-C_6H_3(CF_3)_2]_4} gave the classical hydride complex {[PhBP_3]Ir(PMePh_2)H_3}{B[3,5-C_6H_3(CF_3)_2]_4} (6). In addition to the formation of allyl complexes 2 and 3, several C−H activation reactions have been observed; addition of P^(Me)_3 to 2 provided the cyclometalated product {PhB[(CH_2PPh_2)_2(CH_2PPhC_6H_4)]}Ir(H)(PMe_3)(4) and COE. Photolysis of 5 gave PhB[(CH_2PPh_2)_2(CH_2PPhC_6H_4)]}Ir(H)(PMePh_2) (A) and [PhBP_3]Ir(H)(PMePhC_6H_4) (B). Complex 9 catalyzes H/D exchange between COE and benzene-d_6. Metathesis reactions of diiodide 10 with LiBHEt_3 gave [Li(THF)_n]{[PhBP_3]Ir(H)_2I} (14a) and [Li(THF)_n]{[PhBP_3]Ir(H)_3} (15). Comparison of the spectroscopic properties of related [PhBP_3]Ir, Cp^*Ir, and Tp^(Me)_2Ir complexes suggests that relative donating abilities follow the trend [PhBP_3] ≥ Cp^* > Tp^(Me)_2, and structural comparisons indicate that [PhBP_3] is the most sterically demanding ligand.


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http://dx.doi.org/10.1021/om0205086DOIArticle
http://pubs.acs.org/doi/full/10.1021/om0205086PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om0205086PublisherSupporting Information
ORCID:
AuthorORCID
Peters, Jonas C.0000-0002-6610-4414
Tilley, T. Don0000-0002-6671-9099
Additional Information:© 2002 American Chemical Society. Received 26 June 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 thank Dr. Fred Hollander of the UC Berkeley CHEXRAY facility for assistance with the X-ray structure determinations and for solving the structure of 2.
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Issue or Number:20
DOI:10.1021/om0205086
Record Number:CaltechAUTHORS:20170309-101305346
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170309-101305346
Official Citation:Structural and Chemical Properties of Zwitterionic Iridium Complexes Featuring the Tripodal Phosphine Ligand [PhB(CH2PPh2)3]- Jay D. Feldman, Jonas C. Peters, and T. Don Tilley Organometallics 2002 21 (20), 4050-4064 DOI: 10.1021/om0205086
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74974
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:10 Mar 2017 15:44
Last Modified:15 Nov 2021 16:29

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