TITLE

Octahedral perfluoroalkyl complexes of Ir(III) formed by oxidative addition of perfluoroalkyl iodides to Ir(acac)(CO)2

AUTHOR(S)
Hui Huang; Hurubeanu, N. Raluca; Bourgeois, Cheryl J.; Sue-Mei Cheah; Jian Yuan; Rheingold, Arnold L.; Hughes, Russell P.
PUB. DATE
January 2009
SOURCE
Canadian Journal of Chemistry;Jan2009, Vol. 87 Issue 1, p151
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Oxidative addition of primary, secondary, or benzylic perfluoroalkyl iodides (RF–I) to the phosphine free Ir(I) precursor Ir(acac)(CO)2 1 (acac = 2,4-pentanedionato) proceeds smoothly to afford octahedral Ir(III) products Ir(acac)(I)(RF)(CO)2, A combination of X-ray crystallographic studies and solution spectroscopy shows that these products are the result of overall trans-addition of the C–I bond to iridium, probably a result of thermodynamic control; evidence for a kinetic product resulting from net cis-addition is obtained in one case. Treatment of the Ir(III) compounds with AgOTf (Tf = CF3SO3) illustrates that the iodo ligand is replaced by triflate with retention of stereochemistry at Ir. The resulting triflate complexes are inert to displacement by H2O or H2. The Ir(III) products exhibit very high CO stretching frequencies in the IR, indicating that the CO ligands may be non-classical. A quantitative estimation of the degree of backbonding to the CO ligands in these compounds, and a comparison of the π-acceptor properties of CO and fluoroalkyl ligands, is made using an approach based on Density Functional Theory (DFT) and Natural Bond Orbital analyses.
ACCESSION #
36955983

 

Related Articles

  • Reaction of 1,2,3-Selenadiazoles with Phosphines. Arsenyan, P.; Oberte, K.; Rubina, K.; Belyakov, S.; Lukevics, E. // Chemistry of Heterocyclic Compounds;Apr2004, Vol. 40 Issue 4, p503 

    Nucleophilic attack of tributyl- and triphenyiphosphines on 4-phenyl- and 5-ethoxycarbonyl-4-methyl- 1,2,3-selenadiazoles leads to the quantitative formation of selenophosphoranes and substituted acetylenes. The molecular structure of 4-phenyl-1,2,3-selenadiazole was confirmed by X-ray...

  • Reactivity of allenylphosphonates and allenylphosphine oxides toward 9-chloroacridines and acridone- A facile route to new N-substituted acridones. KUMARI, A; SRINIVAS, VENU; KUMARA SWAMY, K // Journal of Chemical Sciences;Nov2013, Vol. 125 Issue 6, p1405 

    Base-mediated addition of acridones to allenylphosphonates/allenylphosphine oxides (OCHCMeCHO)P(O)CH=C=CRR {R = R = Me ( 1), R = R = [ $-{\rm CH}_{2^-}$] ( 2)}, PhP(O)C(H)= C=CRR {R = R = Me ( 3), R = R = [ $-{\rm CH}_{2^-}$] ( 4)} and (EtO)P(O)C(H)=C=CMe ( 5) in DMF results in the regiospecific...

  • A simple synthetic route to the formation of tetracopper(I) 2-mercaptothiazoline compounds – The crystal structures of [Cu4(S-thiaz)4(PEt2Ph)2],... Fuhr, Olaf; Fernandez-Recio, Lucia; Fenske, Dieter // Canadian Journal of Chemistry;Feb2006, Vol. 84 Issue 2, p251 

    Reactions of copper(I) acetate with 2-mercaptothiazoline (HS-thiaz) in the presence of tertiary phosphines lead to the formation of tetranuclear sulphur-bridged copper complexes. Depending on the reaction conditions, isolated clusters ([Cu4(S-thiaz)4(PR3)2] (PR3 = PPh3 (1), PEt2Ph (2), PEt3...

  • Crystal structure of [Pd(P( i-Pr))(acac)]BF. Kuratieva, N.; Tkach, V.; Suslov, D.; Bykov, M.; Gromilov, S. // Journal of Structural Chemistry;Aug2011, Vol. 52 Issue 4, p813 

    A single crystal X-ray diffraction study is carried out for [Pd(P( i-Pr))(acac)]BF, T = 150(2) K. Crystal data: a = 10.2935(4) Å, b = 11.3591(5) Å, c = 13.8728(6) Å, α = 89.154(2)°, β = 68.448(1)°, γ = 85.032(1)°, P-1 space group, V = 1502.75(11) Å, Z = 2, d =...

  • Crystal Structure of 4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane Diiodide. Chekhlov, A. N. // Russian Journal of General Chemistry;Apr2004, Vol. 74 Issue 4, p574 

    The disordered crystal structure of 4'7'13'16'21'24-hexaoxa-1'10-diazoniabicyclo[8.8.8]hexa-cosane diiodide, [H2(2.2.2-Crypt)]2+·2I-, was studied by single crystal X-ray diffraction. The 2.2.2-cryptanddication is disordered, exists in the form of two different conformers A, B randomly...

  • Crystalline forms of silver iodide II. Determination of phase transformations. Vukić, Marija R.; Veselinović, Dragan S.; Marković, Vesna G. // Journal of the Serbian Chemical Society;Aug2007, Vol. 72 Issue 8/9, p857 

    In order to obtain appropriate forms of AgI (β- and γ-), a procedure was developed to synthesize AgI at room temperature (23 °C), whereby samples of varying crystallographic purity and of varying crystallographic contents of the different forms were obtained. This paper presents the...

  • Synthesis, characterization, and reaction pathways for the formation of a GMP adduct of a cytotoxic thiocyanato ruthenium arene complex. Fuyi Wang; Habtemariam, Abraha; van der Geer, Erwin P. L.; Deeth, Robert J.; Gould, Robert; Parsons, Simon; Sadler, Peter J. // Journal of Biological Inorganic Chemistry;Sep2009, Vol. 14 Issue 7, p1065 

    The organoruthenium complex [(?6-hmb)Ru(en)(Cl)][PF6] (hmb is hexamethylbenzene, en is ethylenediamine) undergoes facile aquation and then reacts with KSCN in unbuffered solution to give the S-coordinated thiocyanato product [(?6-hmb)Ru(en)( S-SCN)]+ which slowly converts to the...

  • Structural and Thermodynamic Properties of Selective Ion Binding in a K Channel. Lockless, Steve W.; Ming Zhou; MacKinnon, Roderick // PLoS Biology;May2007, Vol. 5 Issue 5, pe121 

    Ion selectivity of the KcSA K+ channel is assessed through a combination of thermodynamic measurements of ion binding and structural analysis of ion-bound and ion-free conformations.

  • Crystal Structure and Thermodynamic Properties of N, N-dimethylnorephedrine Hydrochloride (C11H18NOCl)(s). You-Ying Di; Yu-Xia Kong; Wei-Wei Yang; Da-Qi Wang; Zhi-Cheng Tan // Acta Chimica Slovenica;2009, Vol. 56 Issue 2, p392 

    Crystal structure of N, N-dimethylnorephedrine hydrochloride (C11H18NOCl) (s) has been determined by an X-ray crystallography. The compound is orthorhombic P212121. Unit cell parameters are α = 7.2486(19) Å, b = 9.674(3) Å, c = 16.952(5) Å; γ = 90°, α = 90°, α =...

Share

Read the Article

Courtesy of VIRGINIA BEACH PUBLIC LIBRARY AND SYSTEM

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics