Ylide Complexes Research Articles

Acetylen als Baustein für Carben- und Vinylidenliganden am Chrom

The photo-induced reaction of the ArCr(CO) 3 (Ar  η 6-C 6H 6, η 6-C 6H 3Me 3, η 6-C 6Me 6) complexes with acetylene, C 2H 2, yields the acetylene complexes Ar(CO) 2Cr(C 2H 2) (I). The mesitylene complex, η 6-C 6H 3Me 3(CO) 2Cr(C 2H 2), reacts with various phosphines PR 3 (R  Me, Et, nBu) to give the phosphine complexes η 6-C 6H 3Me 3(CO) 2Cr(PR 3) and the ylide complexes η 6-C 6H 3Me 3(CO) 2Cr-[(CHCH(PR 3)] and η 6-C 6H 3Me 3(CO) 2Cr[C(PMe 3)CH 2]. The protonation of η 6-C 6-H 3Me 3(CO) 2Cr[CHCH(P nBu 3)] with HBF 4 results in the formation of the cationic carbene complex &[;η 6-C 6H 3Me 3(CO) 2Cr[CHCH 2(P nBu 3)]&];BF 4. The acetylene complexes I add NHMe 2 to give the aminocarbene complexes Ar(CO) 2Cr[C(Me)NMe 2].

ChemInform Abstract: Reactions of Pentafluorophenyl(ylide)silver(I) or ‐gold(I) Complexes with Chlorobis(pentafluorophenyl)thallium(III).

AbstractThe Tl title compound (I) reacts with the Ag ylide complexes (II) to give AgCl and the air‐ and moisture stable Tl ylide complexes (III).

Oxidative addition of nitroalkanes to dinuclear gold(I) ylide complexes. The characterization by x-ray crystallography of Au2(ylide)2(NO2)2, a nitro complex of gold(II)

Le complexe ylure d'or I: [Au((CH 2 ) 2 PPh 2 )] 2 reagit avec des nitroalcanes pour donner un complexe d'or II: [Au((CH 2 ) 2 PPh 2 )NO 2 ] 2 . On etudie la structure cristalline de ce dernier

ChemInform Abstract: Recoil‐Free Fraction of γ‐Resonance in 197Au Moessbauer Spectroscopy. Findings from Measurements of Polynuclear Mixed‐Valent Ylide Complexes

ChemInformVolume 19, Issue 5 Physical Organic Chemistry ChemInform Abstract: Recoil-Free Fraction of γ-Resonance in 197Au Moessbauer Spectroscopy. Findings from Measurements of Polynuclear Mixed-Valent Ylide Complexes H. SCHMIDBAUR, Phys.-Dep., TU Muenchen, D-8046 GarchingSearch for more papers by this authorC. HARTMANN, Phys.-Dep., TU Muenchen, D-8046 GarchingSearch for more papers by this authorF. E. WAGNER, Phys.-Dep., TU Muenchen, D-8046 GarchingSearch for more papers by this author H. SCHMIDBAUR, Phys.-Dep., TU Muenchen, D-8046 GarchingSearch for more papers by this authorC. HARTMANN, Phys.-Dep., TU Muenchen, D-8046 GarchingSearch for more papers by this authorF. E. WAGNER, Phys.-Dep., TU Muenchen, D-8046 GarchingSearch for more papers by this author First published: February 2, 1988 https://doi.org/10.1002/chin.198805045Read 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 onEmailFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume19, Issue5February 2, 1988 RelatedInformation

ChemInform Abstract: Isovalent and Mixed‐Valent Ylide Complexes of Gold: Synthesis of Trinuclear Compounds with Double Paddle‐Wheel Structure.

AbstractThe reaction of gold(II) complexes (I) with ylides depends on the ratio of reactants.

Transition metal-cyanocarbon chemistry: VII. Reactions of mono- and di-cyanoacetylenes with tricarbonylcyclopentadienylmethylthiolatotungsten(II). Formation of phosphorus ylide complex [(C 5H 5)(CO) 2[formula omitted](CN)SCH 3)]. Crystal structure of [(C 5H 5)(CO) 2(P(C 6H 5) 3)-W(C(O)C(CN)CHSCH 3)·CH 2Cl 2

Reactions of (C 5H 5)(CO) 3W(SMe) with cyano-activated alkynes RCCCN with R  H or CN give heterometallacyclic complexes (C 5H 5)(CO) 2 W(C(O)C(CN)C(R)S Me) (R  H ( 2) or CN ( 6)) or for R  H, an insertion σ-vinylic complex [(C 5H 5)(CO) 3W(CHC(CN)SMe)] ( 3). Irradiation of 3 in the presence of PPh 3 in THF gives the ylide complex (C 5H 5)(CO) 2W(η 2-CH(PPh 3)C(CN)SMe) ( 5), whereas 2 under such conditions gives an η 1-acylic complex [(C 5H 5)(CO) 2PPh 3W(C(O)C-(CN)CHSMe)] ( 4). The structure of 4 has been determined by X-ray diffraction.

Reactions of pentafluorophenyl(ylide)-silver(I) or -gold(I) complexes with chlorobis(pentafluorophenyl)thallium(III)

Chlorobis(pentafluorophenyl)thallium(III) reacts with silver–ylide complexes [Ag(C6F5)(CH2ER3)](ER3= PPh3, PPh2Me, PPhMe2, or AsPh3) to give AgCl and [Tl(C6F5)3(CH2ER3)], whereas the reactions with gold–ylide complexes, [Au(C6F5)(CH2PR3)], lead to gold(III) complexes of the types trans-[Au(C6F5)2Cl(CH2PR3)] and [Au(CH2PR3)2][Au(C6F5)4] which have been isolated and characterized.

Synthesis of pentafluorophenyl(ylide)silver(I) complexes: X-ray structures of two modifications of [Ag(C6F5)(CH2PPh3)

Monomeric silver ylide complexes [Ag(C6F5)(CH2ER3)](ER3= PPh3, PPh2Me, PPhMe2, or AsPh3) can be prepared by the reaction of Ag(CF3CO2) with Li(C6F5) and [ER3Me][CF3CO2]. The free ylides CH2PPh3, CH2PPh2Me, or CH(CO2Me)PPh3 react with Ag(C6F5) or AgClO4 to afford [Ag(C6F5)(ylide)] or [Ag(CH2PPh3)2]ClO4 respectively. Several novel ylide-transfer reactions from silver ylides to other silver or gold centres are reported. The structures of two forms of [Ag(C6F5)(CH2PPh3)] have been established. The molecules differ mainly in the orientation of one phenyl ring. The C6F5 groups are highly distorted at the ipso carbon [C–C–C 113.1 (5) and 112.5(5)°].

Addition of halogens to [{Au(CH2)2PPh2}2RX] complexes. The structures of cis,trans-[{Au(CH2)2PPh2}2(CH2CF3)Br3] and trans,trans-[{Au(CH2)2PPh2}2(CHCl2)Br2Cl

The syntheses and X-ray structures of the dinuclear gold(III) phosphorus ylide complexes cis,trans-[{Au(CH2)2PPh2}2(CH2CF3)Br3] and trans,trans-[{Au(CH2)2PPh2}2(CHCl2)Br2Cl] are reported. In CDCl3, cis,trans-[{Au(CH2)2PPh2}2(CH2CF3)Br3] is stable towards isomerisation after 4 d at 25°C. The cis,trans and trans,trans complexes are obtained from the oxidative addition of Br2 to the gold(II) alkyl halide complex [{Au(CH2)2PPh2}2(CH2CF3)I] and the reaction of [{Au(CH2)2PPh2}2] with an excess of CHCl2Br, respectively. Crystallographic data: cis,trans-[{Au(CH2)2PPh2}2(CH2CF3)Br3]·(C2H5)2O, triclinic, space group P(no. 2), a= 10.995(3), b= 13.056(3), c= 15.028(3)Aα= 93.35(2), β= 105.45(2), γ= 109.43(2)°, Z= 2, R= 0.058, R′= 0.058 for 2 782 unique reflections with |F0|2 > 3σ(|F0|2); trans,trans-[{Au-(CH2)2PPh2}2(CHCl2)Br2Cl] triclinic, space group P(no. 2), a= 11.716(4), b= 14.634(4), c= 9.619(3)A, α= 94.44(3), β= 96.26(3), γ= 83.41(3)°, Z= 2, R= 0.081, R′= 0.086 for 2 254 reflections with |F0|2 > 3σ(|F0|2). Both complexes contain four-co-ordinate gold atoms in the +3 oxidation state with an approximate square-planar arrangement of the bridging lignds. The metal atoms are separated by non-binding distances of 3.103(1) and 3.070(9)A respectively.

Isovalent and Mixed‐Valent Ylide Complexes of Gold: The Synthesis of Trinuclear Compounds Having Double Paddlewheel Structure

Isovalent and Mixed‐Valent Ylide Complexes of Gold: The Synthesis of Trinuclear Compounds Having Double Paddlewheel Structure

Synthesis of silver(I) complexes with carbonyl-stabilized phosphorus ylides: crystal structures of two [Ag{;CH(PPh 3)C(O)R}; 2] + derivatives

Reactions between AgX (X  ClO 4, NO 3) and ylides of the type Ph 3PCHC(O)R (R &.dbnd; Me, Ph, OMe, OPh) in the molar ratio sol1 2 lead to complexes [Ag{;CH(PPh 3)C(O)R}; 2]X; X-ray structure determinations have been carried out on two such complexes (R &.dbnd; OEt, X &.dbnd; ClO 4 and R &.dbnd; OPh, X &.dbnd; NO 3). Two of the silver ylide complexes react with [Au(acac)(PPh 3)] (acac &.dbnd; acetylacetonate) in the molar ratio sol1 2 to give complexes [Ag{;C(PPh 3)(CO 2R)(AuPPh 3)};]ClO 4 (R &.dbnd; Me, Et).

Synthesis and reactions of some sulfur ylide complexes of palladium

The iodo-bridged sulfur ylide complex [Pd(μ-I)((CH 2) 2(SO)(CH 3))] 2 ( 1) when treated with dithiolates, acetylacetone and various Lewis bases gave [Pd((CH 2) 2(SO)(CH 3))(S ∼ S)] (S ∼ S = S 2CN(C 2H 5) 2, S 2COC 2H 5 and S 2P(OC 2H 5) 2), [Pd((CH 2) 2(SO)(CH 3))(acac)] (acac = acetylacetonate) and [PdI((CH 2) 2(SO)(CH 3))(base)]a (base = PPh 3, (P(OMe) 3, P(OPh) 3 and C 5H 5N). In the presence of a phase transfer catalyst (PTC). The reactions rates and yields were greatly increased. Reaction of several related sulfur ylide complexes with I 2, HI or aqueous NaOH gave 1. The single crystal structure of [Pd((CH 2) 2(SO)(CH 3)) 2] was determined (orthorhombic, Pbcn, a 13.379(2), b 8.081(1), c 9.048(2) Å, V 978.2 Å 3, Z = 4). The compound has a rather long PdCH 2 bond (2.096(1) Å, mean).

Reactivity and mechanism in the reactions of platinacyclobutanes to give alkene or ylide complexes: evidence for .alpha.-elimination

Reactivity and mechanism in the reactions of platinacyclobutanes to give alkene or ylide complexes: evidence for .alpha.-elimination

Reactive Bis(cyclopentadienyl)niobium Moiety: Synthesis of the First Niobium Phosphorus Ylid Complexes

Abstract Phosphorus ylides are known to form σ-metal-carbon bonds of unusual stability. Bis(cyclopentadienyl)niobium derivatives offer a general synthetic approach to niobium phosphorus ylide complexes, the first to be reported.

ChemInform Abstract: Haloalkyl Complexes of the Transition Metals. Part 5. The Synthesis and Reactions of Some New Pentamethylcyclopentadienyl Halomethyl and Methoxymethyl Complexes of Molybdenum(II) and Tungsten(II) and the X-Ray Crystal Structure of the

Abstract Synthetic routes are described for the new halo- methyl complexes of the type [η-C5Me5M(CO)3- CH2X]. The complexes where M = Mo, X = Cl or OMe and M = W, X = Cl, I, OMe have been fully characterized. Reaction of [η-C5Me5Mo(CO)3CH2Cl] with PPh3 in methanol under reflux or acetonitrile at room temperature gives [η-C5Me5Mo(CO)2(PPh3)- Cl], whereas reaction of [η-C5Me5W(CO)3CH2I] with PPh3 under similar conditions gives the cationic phosphorus ylide complex [η-C5Me5W(CO)3CH2- PPh3]I. The structure of this ylide complex has been determined by X-ray crystallography. The complex crystallizes with half a molecule of CH2Cl2 in the monoclinic space group P21/n with a = 16.616- (8), b = 11.738(6), c = 18.126(9) A, β = 101.74(2)° and Z = 4. The structure was solved and refined to R = 0.076. It confirms the formulation of the compound and the presence of the ylide ligand, WCylide 2.34(2) A, PCylide 1.82(2) A and the WCylideP angle of 119(1)°.

Synthesis and x-ray crystal structures of [Au(CH2)2PPh2]2(CF3)2, [Au(CH2)2PPh2]2(C6F5)2, and [PPN][Au(C6F5)4]: two dinuclear gold(II) ylide complexes containing alkyl and aryl ligands and a tetrakis(pentafluorophenylaurate(III) anion complex

Synthesis and x-ray crystal structures of [Au(CH2)2PPh2]2(CF3)2, [Au(CH2)2PPh2]2(C6F5)2, and [PPN][Au(C6F5)4]: two dinuclear gold(II) ylide complexes containing alkyl and aryl ligands and a tetrakis(pentafluorophenylaurate(III) anion complex

Emission and electrochemical studies of 2-pyridylcarbonylmethylide-rhenium(I) complexes

Re(I)Br(CO) 3(2-pyridylcarbonylmethylide) and Re(I)Br(CO) 3(2-acetylepyridine) were prepared by reactions of Re(I)Br(CO) 5 with 2-pyridylcarbonylmethylides, C 5H 4NC(O)−CH+Z [+Z = +PPh 3 (Y p), +AsPh 3 (Y As), +SMe 2 (Y s) and +NC 5H 4R−4 (Y N-R; R = CN, Ph, H and Me)], and 2-acetylpyridine. These complexes are concluded to assume an octahedral geometry containing the chelation by the carbonyl oxygen and pyridyl nitrogen atoms and the facial-coordination of metal carbonyl groups on the basis of IR and 1H-NMR spectra. Although the 2-acetylpyridine complex gave no emission, the Y p, Y As, and Y s complexes showed an emission due to the metal-to-ligand charge transfer (MLCT) transition at 77 K in MeOH/EtOH (1 : 4 v/v). On the other hand, the Y N-R complexes showed emissions due to both the MLCT and the intraligand CT transitions. All the present ylide complexes were oxidized at +0.71 to +0.82 V vs Ag/Ag + in acetonitrile. The Y p, Y As, and Y S complexes were reduced at − 1.91 to − 2.00 V, while reduction of the Y N-R complexes occurred on the pyridinium ring of the ylides at less negative potentials ( − 1.68 to − 1.04 V).

Haloalkyl complexes of the transition metals: IV. The formation of a cationic ylide complex of platinum(II) from a chloromethylplatinum(II) complex and the crystal structures of cis-[Pt(CH 2PPh 3)X(PPh 3) 2]I (X = Cl or I)

The reactions of Pt(PPH 3) 4 and Pt(C 2H 4)(PPh 3) 2 with CH 2ClI have been investigated. The product of the reaction of Pt(PPh 3) 4 with CH 2ClI is the cationic ylide complex cis-[Pt(CH 2PPh 3)Cl(PPh 3)2][I], whereas the reaction of Pt(C 2H 4)-(PPh 3) 2 gives the oxidative addition product Pt(CH 2Cl)I(PPh 3) 2. Reaction of cis- or trans-Pt(CH 2Cl)I(PPh 3) 2] with PPh 3 gives the complex cis-[Pt(CH 2PPh 3)-Cl(PPh 3) 2][I]. The structures of the complexes cis-[Pt(CH 2PPh 3X(PPh 3) 2][I] (where X = Cl or I) have been determined by X-ray crystallography. Both complexes crystalize in the monoclinic space group P2 1/ n. For X = Cl a 1388.6(7), b 2026.7(10), c 1823.9(9) pm, β 96.51(2)° and R converged to 0.075 for 3542 observed reflections; structural parameters Pt-Cl 240(1), Pt-C(3) 212(2), Pt-P(2) ( trans to Cl) 235(1) and Pt-P(1) ( trans to CH 2PPh 3) 233(1) pm; Cl-Pt-C(3) 86.9(5), C(3)-Pt-P(2) 91.8(5), P(2)-Pt-P(1) 97.0(2) and P(1)-Pt-Cl 85.1(2)°. For X = I, a 1379.4(7), b 2044.4(10), c 1840.0(9) pm, β 96.09(2)° and R converged to 0.071 for 4333 observed reflections; structural parameters Pt-I 266(1), Pt-C(3) 212(2), Pt-P(2) ( trans to I) 226(1) and Pt-P(1) ( trans to CH 2PPh 3 233(1) pm; I-Pt-C(3) 87.2(5), C(3)-Pt-P(2) 91.5(5), P(2)-Pt-P(1) 96.5(2) and P(1)-Pt-I 85.6(1)°. Some other complexes of the type cis-[Pt(CH 2PPh 3)X(PPh 3) 2]Y are also described.

The synthesis of sulfur ylide complexes of palladium, zinc and copper in water

Various sulfur ylide complexes have been prepared by a simple technique, using simple starting materials, in water. Thus in aqueous solution, the sulfur ylide complexes [Pd(μ-I)((CH2)2(SO)(CH3))]2 and PdI[(CH2(SO)-(CH32][(CH3)] were obtained by the reaction of (NH4)2PdCl4 with [(CH3)3(SO)]I in the presence of NaOH in water. Further reactions of the first product with [(CH3)3(SO)]I in basic solution gave Pd[(CH22(SO)(CH3)]2 and [Pd((CH2)(SO)(CH3)2)(CH2)2(SO)(CH3))]I under various conditions. Reactions of ZnCl2 and CUCl with [(CH3)3(SO)]I in NaOH solution afforded compounds containing nonstoichiometric amounts of sulfur ylide. One of the palladium compounds, pdI[(CH2)(SO)(CH32][(CH2)(SO)(CH3)], was subjected to X-ray, single crystal structure, analysis. The compounds crystallizes in the space group P21c with a 11.033(4), b 11.981(5), and c 9.407(3) Å, β 103.23(1)°, Z = 4. Final R was 0.064 for 1870 observed reflections. The compound contained a monodentate sulfoxonium ylide and a bidentate sulfoxonium double-ylide.

Transition-metal sulfur ylide complexes. 23. Methylene transfer from sulfur ylides to transition-metal complexes: a parallel between sulfur ylides and diazomethane to organometallic chemistry

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition-metal sulfur ylide complexes. 23. Methylene transfer from sulfur ylides to transition-metal complexes: a parallel between sulfur ylides and diazomethane to organometallic chemistryLothar Weber and Ewald LueckeCite this: Organometallics 1986, 5, 10, 2114–2116Publication Date (Print):October 1, 1986Publication History Published online1 May 2002Published inissue 1 October 1986https://doi.org/10.1021/om00141a031RIGHTS & PERMISSIONSArticle Views154Altmetric-Citations8LEARN 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 (428 KB) Get e-Alerts Get e-Alerts