Oxidative Addition Of Alkyl Halides Research Articles

Stereoselectivity in Organometallic Reactions: Oxidative Addition of Alkyl Halides to Platinum(II)

The ligands cis- and trans-1,2-(NCHC6H5)2C6H10 (trans, 1; cis, 2) underwent cyclometalation of one phenyl substituent on reaction with [Pt2Me4(μ-SMe2)2] (3) to give CH4 and chiral platinum(II) comp...

ChemInform Abstract: Oxidative Addition of Alkyl Halides to Rhodium(I) and Iridium(I) Dicarbonyl Diiodides: Key Reactions in the Catalytic Carbonylation of Alcohols

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Oxidative Addition of Alkyl Halides to Rhodium(I) and Iridium(I) Dicarbonyl Diiodides: Key Reactions in the Catalytic Carbonylation of Alcohols

Oxidative Addition of Alkyl Halides to Rhodium(I) and Iridium(I) Dicarbonyl Diiodides: Key Reactions in the Catalytic Carbonylation of Alcohols

Thermal and photochemical oxidative addition of alkyl halides to the cyclometalated complex cis-bis[2-(2-thienyl)pyridine]platinum(II)

The homoleptic, cyclometalated complex cis-bis[2-(2'-thienyl)pyridine] platinum(II) (1, Pt(2'-thpy) 2 ) undergoes thermal or photochemical oxidative addition (TOA or POA) reactions with a wide range of alkyl halides. These reactions are found to be highly stereoselective, yielding in most cases Pt(IV) complexes with the halide and the σ-bonded C(alkyl) atom in the cis position, in a C,C,C-fac arrangement. In some cases, trans addition of R-X was observed, followed by trans→cis isomerization, either at room temperature or on heating. Extensive use was made of 1 H NMR spectroscopy in assigning the configurations, and the 2-D COSY spectra, measured for a few of the Pt(IV) complexes, were helpful in making the chemical shift assignment

Preparation and reactivity of dinuclear Ru II complexes with bridging thiolate ligands [Cp★Ru(μ-SR) 2RuCp★] (Cp★  η 5-C 5Me 5; R  iPr, tBu, 2,6-Me 2C 6H 3).Oxidative addition of alkyl halides at the diruthenium center

Reactions of [Cp★RuCl] 4 (Cp★  η 5-C 5Me 5) with NaSR (R  iPr, tBu, 2,6-Me 2C 6H 3) in THF afforded dinuclear Ru II complexes with two bridging thiolate ligands [Cp★Ru(μ-SR) 2RuCp★] ( 3). An X-ray analysis of 3c (R = 2,6-Me 2C 6H 3) has disclosed the folded Ru 2S 2 core structure with two equatorial C 6H 3Me 2-2,6 groups in a solid state, while the results of variable-temperature 1H NMR study are diagnostic of the fluxional nature of complexes 3 in solution resulting from the Ru 2S 2 ring inversion. Complex 3a (R  iPr) underwent oxidative addition of RX (R  PhCH 2CH 2 or PhCH 2, X  Br; R  Me or Et, X  I) and H 2 across the Ru 2 center to give [Cp★RuR(μ-S iPr) 2RuCp★X] ( 7) and [Cp★RuH(μ-S iPr) 2RuCp★H], respectively. The structure of 7a (R  PhCH 2CH 2, X  Br) has been determined by X-ray crystallography. Crystal data for 3c: space group P4 2/ mnm, a = 15.307(4) Å, c = 16.070(4) Å, V = 3765(2) Å 3, Z = 4; 7a: space group P2 1/ c, a = 10.348(2) Å, b = 15.113(2) Å, c = 22.340(5) Å, β = 93.10(2)°, V = 3488(1) Å 3, Z = 4.

SN2 or Electron Transfer?? A new technique discriminates the mechanisms of oxidative addition of alkyl halides to corrinato‐ and porphyrinatocobalt(I)

AbstractA fast electrochemical technique for the discrimination of one‐ and two‐electron mechanisms in the oxidative addition of alkylating agents (RX) to corrinato‐ and porphyrinatocobalt(I) ([CoIL]) is described. It is based on single‐scan voltammograms of [CoIIL] in the presence of RX and variable amounts of the radical trap acrylonitrile. In the first part of the voltammogram, [CoIIL] is reduced, and fast oxidative addition of RX to [CoIL] is triggered. If the reaction proceeds via a two‐electron mechanism, [RCoIIIL] is formed independently of acrylonitrile concentration, but if a transient free radical R is involved, R is competitively trapped by acrylonitrile and [CoIIL] to yield, at high enough acrylonitrile concentration, exclusively the olefin‐inserted [RCNCoIIIL]. [RCNCoIIIL] is reducible in the intermediate potential range, [RCoIIIL] at the negative end of the single‐scan voltammogram. Hence, from the appearance of the reduction waves due to [RCNCoIIIL] and [RCoIIIL], the mechanism of oxidative addition of RX to [CoIL] is easily deduced. The method is applied to the study of the mechanistic borderline of oxidative addition using a series of 15 RX and 4 [CoL]'s, i.e. cobalamin (Cbl), heptamethyl cobyrinate (‘Cby’), (tetraphenylporphyrinato) cobalt ([Co(tpp])), and (octaethylporphyrinato) cobalt ([Co(oep)]). All non‐activated primary alkyl iodides and bromides exhibit, at room temperature, pure two‐electron mechanisms with all [CoIL]'s, except neopentyliodide with Cb1I and ‘Cby’I. All secondary alkyl iodides involve free radicals with Cb1I and ‘Cby’I, but a pure two‐electron mechanism or a mixed one‐electron two‐electron mechanism with [CoI(tpp)] and [CoI(oep)]. The mechanistic switch from a two‐electron to a one‐electron mechanism for increasingly sterically demanding RX's occurs earlier with the supernucleophilic Cb1I and ‘Cby’I than with [CoI(tapp)] and [CoI(oep)].

ChemInform Abstract: Oxidative Addition of Alkyl Halides to the Dinuclear Gold(I) Phosphorus Ylide Complexes. Crystal and Molecular Structures of (Au2(CH2)2PPh2)2and (Au(CH2)2PPh2)2(CH3)Br

Chemischer InformationsdienstVolume 17, Issue 36 Reviews ChemInform Abstract: Oxidative Addition of Alkyl Halides to the Dinuclear Gold(I) Phosphorus Ylide Complexes. Crystal and Molecular Structures of (Au2(CH2)2PPh2)2 and (Au(CH2)2PPh2)2(CH3)Br J. D. BASIL, J. D. BASILSearch for more papers by this authorH. H. MURRAY, H. H. MURRAYSearch for more papers by this authorJ. P. JUN. FACKLER, J. P. JUN. FACKLERSearch for more papers by this authorJ. TOCHER, J. TOCHERSearch for more papers by this authorA. M. MAZANY, A. M. MAZANYSearch for more papers by this authorT. J. DELORD, T. J. DELORDSearch for more papers by this authorB. T. BANCROFT, B. T. BANCROFTSearch for more papers by this authorH. KNACHEL, H. KNACHELSearch for more papers by this authorD. S. DUDIS, D. S. DUDISSearch for more papers by this author J. D. BASIL, J. D. BASILSearch for more papers by this authorH. H. MURRAY, H. H. MURRAYSearch for more papers by this authorJ. P. JUN. FACKLER, J. P. JUN. FACKLERSearch for more papers by this authorJ. TOCHER, J. TOCHERSearch for more papers by this authorA. M. MAZANY, A. M. MAZANYSearch for more papers by this authorT. J. DELORD, T. J. DELORDSearch for more papers by this authorB. T. BANCROFT, B. T. BANCROFTSearch for more papers by this authorH. KNACHEL, H. KNACHELSearch for more papers by this authorD. S. DUDIS, D. S. DUDISSearch for more papers by this author First published: September 9, 1986 https://doi.org/10.1002/chin.198636353Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume17, Issue36September 9, 1986 RelatedInformation

Oxidative addition of alkyl halides in the presence of alkenes and the rate of addition of an alkyl radical to a platinum(II) complex

Le dimethyl (phenanthroline-1,10) platine(II) reagit avec l'iodure d'isopropyle ou de t-butyle, RI, en presence d'alcenes [CH 2 =CHX ou X=CN,CHO ou C(=O)Me] pour donner les complexes du platine(IV) [PtIMe 2 (CHXCH 2 R)(phen)]

Synthesis and configurations of 2-methyl-1-organo-1-halo-1-telluracyclopentanes

Some new cyclic telluronium salts (C 5H 10TeRX: R = CH 3, CH 3Cl 3, X = I; R = CH 2Ph, X = Br) have been prepared by oxidative addition of alkyl halides to 2-methyl-1-telluracyclopentane. The cis/ trans ratio in the product mixture was determined by 1H NMR spectroscopy.

Alkylperoxoplatinum(IV) complexes formed by oxidative addition of alkyl halides in the presence of oxygen: the mechanism of reaction and the structure of trans-iodo(isopropylperoxo)dimethyl(1,10-phenanthroline)platinum(IV)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAlkylperoxoplatinum(IV) complexes formed by oxidative addition of alkyl halides in the presence of oxygen: the mechanism of reaction and the structure of trans-iodo(isopropylperoxo)dimethyl(1,10-phenanthroline)platinum(IV)George. Ferguson, Patrick K. Monaghan, Masood. Parvez, and Richard J. PuddephattCite this: Organometallics 1985, 4, 9, 1669–1674Publication Date (Print):September 1, 1985Publication History Published online1 May 2002Published inissue 1 September 1985https://doi.org/10.1021/om00128a032RIGHTS & PERMISSIONSArticle Views231Altmetric-Citations44LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (760 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Synthese et caracterisation par RMN 1H d'alkyl(aryl)ferriporphyrines a liaison σ metalcarbone

A series of alkyl(aryl)iron(III) porphyrins with a metalcarbon σ bond has been prepared either by action of an organomagnesium compound on iron(III) chloride porphyrins or by oxidative addition of alkyl halides to iron(I) porphyrins. 1H NMR data have been used to characterize the products obtained.

Solution studies of triorganotelluronium salts

Evidence for telluronium ylid formation via the salt method is obtained for Ph 2Te(CH 2COPh)Br, but generally telluronium salts (aryl) 2Te(CH 2R)X rapidly dissociate in chloroform solution to (aryl) 2Te and RCH 2X. The relative rates of dissociation of Ph 2(CH 3)TeX in CHCl 3 are: X = I > Br ∼ NCS > Cl > PhCOO. Conductivity and 1H NMR data suggest the salts Ph 2(CH 3)TeX to be covalent and at least dimeric in CHCl 3, but more ionic in DMSO and, to a lesser extent, a DMF. IR data indicate association in solid Ph 2(CH 3)Tel. Kinetic data show that the reaction of CH 3I with excess Ph 2Te (solvent) affords an equilibrium mixture of ionic and covalent forms of Ph 2(CH 3)Tel, the ionic species being formed via the covalent one. Spin trapping experiments with phenyl(t-butyl)nitrone indicate that oxidative addition of alkyl halides to Ph 2Te and redcutive elimination of CH 3SCN from Ph 2 (CH 3)Te(NCS) proceed via radical pathways. A mechanism is proposed for oxidative addition which involves the preformation of a charge transfer complex of RX (alkyl halide) and diphenyltelluride.

A Mechanistic Investigation of the Oxidative Addition of Alkyl Halides to Palladium Atoms

Palladium atoms (vapor) have been cocondensed at low temperature with a series of alkyl halides. Oxidative addition to form RMX occurs. Trapping experiments, free radical scavenging experiments, and decomposition product distributions suggest that the metal atom CX bond insertion occurs direclty via a caged radical pair.

Oxidative addition of alkyl halides to zero-valent palladium complexes. Mechanisms

Oxidative addition of alkyl halides to zero-valent palladium complexes. Mechanisms

Halide catalysis of the oxidative addition of alkyl halides to rhodium(I) complexes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHalide catalysis of the oxidative addition of alkyl halides to rhodium(I) complexesDenis ForsterCite this: J. Am. Chem. Soc. 1975, 97, 4, 951–952Publication Date (Print):February 1, 1975Publication History Published online1 May 2002Published inissue 1 February 1975https://doi.org/10.1021/ja00837a075RIGHTS & PERMISSIONSArticle Views193Altmetric-Citations57LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (274 KB) Get e-Alerts Get e-Alerts

Stereochemistry of oxidative addition of alkyl halides to palladium(0) complexes

Stereochemistry of oxidative addition of alkyl halides to palladium(0) complexes

Free radicals as intermediates in the oxidative addition of alkyl halides to platinum(0)

Free radicals are implicated in the oxidative addition of an alkyl halide RX (MeI, CD3I, EtI, or PhCH2Br) to Pt(PPh3)3, as shown by identifying (e.s.r.) the derived nitroxide But(R)NO. using ButNO as a spin trap; a non-chain mechanism is proposed, with the formation of [PtIX(PPh3)2]· as rate limiting.

The formation of pentacyanohydridorhodate(III): kinetic and spectral evidence for the oxidative addition of hydrogen cyanide to the intermediate tetracyanorhodate(I)

In the reaction of NaCN with [Rh(CO)2Cl]2 evidence has been found for the formation of a transient intermediate which is probably Rh(CN)43–; the u.v.–visible spectrum of the intermediate is reported. The decay of the intermediate, studied by the stopped-flow method, has been identified as the oxidative addition of HCN to Rh(CN)43– to form Rh(CN)5H3–; the pH dependence and isotope effect of D2O on the rate constant have been examined. The oxidative addition of alkyl halides to Rh(CN)43–, Rh(CN)3CO2–, and Rh(CN)2(CO)2– is reported and the mechanism of formation of acyl rhodium(III) compounds Rh(CN)5(COCH3)3– is discussed.

Iron catalysis in the reaction of grignard reagents with alkyl halides

The stoichiometry and kinetics of the reaction between various Grignard reagents and alkyl halides with an iron catalyst have been examined in tetrahydrofuran solutions. The catalytic iron species is produced in situ by the reduction of iron-(II) and -(III) halides by Grignard reagent. The activity of the catalyst is dependent on the solvent and deactivation by ageing is attributed to aggregation of the catalytic iron species. The catalytic process is postulated to occur via a redox cycle, in which the oxidative addition of alkyl halide to a reduced form of iron is followed by disproportionation of the alkyliron intermediates to regenerate the iron catalyst. Alkyl radicals are formed in the step involving oxidative addition. Thus, styrenepreferentially scavenges only that alkyl moiety derived from the alkyl halide. Side reactions involving the catalytic exchange of Grignard reagent with alkene and alkyl halide are also described.

Oxidative addition of alkyl halides to iridium(I) complexes; the inversion of configuration at carbon

The oxidative addition of an alkyl halide to a d8 square planar IrI complex is shown to proceed with inversion of configuration at carbon.