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Synthesis and Characterization of [Ir_2(TMB)_4H_2][B(C_6H_5)_4]_2·CH_3C_6H_5

Smith, David C. and Marsh, Richard E. and Schaefer, William P. and Loehr, Thomas M. and Gray, Harry B. (1990) Synthesis and Characterization of [Ir_2(TMB)_4H_2][B(C_6H_5)_4]_2·CH_3C_6H_5. Inorganic Chemistry, 29 (3). pp. 534-538. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20171107-152617829

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Abstract

The ^3(dσ *pσ) excited state of Ir_2(TMB)_4^(2+) (TMB = 2,5-diisocyano-2,5-dimethylhexane) reacts with hydrogen atom donors to give Ir_2(TMB)_4H_2^(2+) (Ir_2H_2). This d^7-d^7 dihydride has been isolated as a tetraphenylborate salt: v(Ir-H) 1940 cm^(-1), v(Ir-Ir) 136 cm^(-1). [Ir_2(TMB)_4H_2] [B(C_6H_5) _4]_2·CH_3C_6H_5, Ir_2C_(95)H_(114)N_8B_2, crystallizes in the monoclipic system, space group P2_1/c (No. 14), with a = 10.54 (2) Å, b = 31.02 (4) Å, and c = 27.05 (4) Å, β = 91.57 (3)°, V = 8841 (3) Å^3, and Z = 4. The Ir-Ir separation is 2.920 (2) Å, approximately 0.3 Å shorter than Ir-Ir in the d^8 dimer (lr_2) but ~0.1 Å longer than in the diiodide, Ir_2(TMB)_4I_2^(2+). The reaction of Ir_2H_2 with styrene gives Ir_2 and ethylbenzene.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/ic00328a039DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic00328a039PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic00328a039PublisherSupporting Information
ORCID:
AuthorORCID
Gray, Harry B.0000-0002-7937-7876
Alternate Title:Synthesis and characterization of tetrakis(2,5-diisocyano-2,5-dimethylhexane)dihydridodiiridium(2+) tetraphenylborate.cntdot.toluene
Additional Information:© 1990 American Chemical Society. Received June 28, 1989. D.C.S. thanks the Sun Co. for a graduate fellowship. This research was supported by National Science Foundation Grant CHE84-19828.
Funders:
Funding AgencyGrant Number
Sun Co.UNSPECIFIED
NSFCHE84-19828
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics7963
Issue or Number:3
Record Number:CaltechAUTHORS:20171107-152617829
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20171107-152617829
Official Citation:Synthesis and characterization of tetrakis(2,5-diisocyano-2,5-dimethylhexane)dihydridodiiridium(2+) tetraphenylborate.cntdot.toluene. David C. Smith, Richard E. Marsh, William P. Schaefer, Thomas M. Loehr, and Harry B. Gray. Inorganic Chemistry 1990 29 (3), 534-538. DOI: 10.1021/ic00328a039
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:83043
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Nov 2017 23:47
Last Modified:22 Nov 2019 09:58

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