Cationic Carbyne Complexes Research Articles

Unusual Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Reactive Salts [Et3NH][(μ-CO)(μ-RS)Fe2(CO)6]. A Route to Dimetal Bridging Carbene Complexes

The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2Mn⋮CC6H5]BBr4 (1), with the reactive salt [Et3NH][(μ-CO)(μ-n-C4H9S)Fe2(CO)6] (3) in THF at low temperature gave the dimetal bridging carbene complex [MnFe{μ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (8) and [Fe(CO)3(n-C4H9S)]2 (7). 1 reacted with [Et3NH][(μ-CO)(μ-C6H5S)Fe2(CO)6] (4) to give the bridging carbene complex [MnFe{μ-C(C6H5S)C6H5}(CO)5(η-C5H5)] (11) and the manganese phenylthiocarbene complex [η-C5H5(CO)2MnC(C6H5S)C6H5] (12), besides [Fe(CO)3C6H5S]2 (10). 1 also reacted with [Et3NH][(μ-CO)(μ-p-CH3C6H4S)Fe2(CO)6] (5) to yield [Fe(CO)3(p-CH3C6H4S)]2 (13) and the bridging carbene complex [MnFe{μ-C(p-CH3C6H4S)C6H5}(CO)5(η-C5H5)] (14). Analogous reactions of the cationic rhenium carbyne complex [η-C5H5(CO)2Re⋮CC6H5]BBr4 (2) with 3 and 4 gave the corresponding bridging carbene complexes [ReFe{μ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (16) and [ReFe{μ-C(C6H5S)C6H5}(CO)5(η-C5H5)] (17) and the phenylthiocarbene complex [η-C5H5(CO)2ReC(C6H5S)C6H5] (18), respectively. The structures of 8, 11, 12, 16, and 18 have been established by X-ray diffraction studies.

Reactions of cationic carbyne complexes of manganese and rhenium with metal carbonyl anions

Treatment of [(η-C5H5)(OC)2MnCC6H5]BBr4 1 and [(η-C5H5)(OC)2ReCC6H5]BBr4 2 with the carbonyl monoanion [Mn(CO)5]– 3 in THF at low temperature afforded the ketenyl bridged complexes [Mn2{µ-C(CO)C6H5}(CO)6(η-C5H5)] 6 and [ReMn{µ-C(CO)C6H5}(CO)6(η-C5H5)] 7 respectively. The analogous reactions of complexes 1 and 2 with [Co(CO)4]– 4 gave corresponding ketenyl bridged complexes [MnCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] 8 and [ReCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] 9 respectively. Complexes 1 and 2 reacted with the carbonyl dianion [W(CO)5]2– 5 to give the dimetal carbene bridged complexes [MnW{µ-C(H)C6H5}(CO)7(η-C5H5)] 10 and [ReW{µ-C(H)C6H5}(CO)7(η-C5H5)] 11 respectively. The structures of complexes 6, 9 and 11 have been established by X-ray diffraction studies.

Unusual reactions of cationic carbyne complexes of manganese and rhenium with [NMe4][HFe(CO)4] to form heteronuclear dimetal carbene-bridged complexes

The reaction of a cationic carbyne complex of manganese [Mn(CPh)(η-C5H5)(CO)2]BBr4 1 with the salt [NMe4][HFe(CO)4] 3 in thf at low temperature gave [Mn(η-C5H5)(CO)3] 4 and a novel dimetal carbene-bridged complex [MnFe{µ-C(H)Ph}(η-C5H5)(CO)5] 5. The cationic rhenium carbyne complex [Re(CPh)(η-C5H5)(CO)2]BBr4 2 similarly reacted with 3 to give [Re(η-C5H5)(CO)3] 6 and [ReFe{µ-C(H)Ph}(η-C5H5)(CO)6] 7. Complex 5 reacted with carbon monoxide gas leading to cleavage of the µ-C–Mn and Mn–Fe bonds to afford 4 and a novel benzene-co-ordinated acyltricarbonyliron complex [Fe(PhCHCO)(CO)3] 8. The reaction of 7 with PPh3 yielded [ReFe{µ-C(H)Ph}(η-C5H5)(CO)5(PPh3)] 9. The structures of complexes 5, 8 and 9 have been established by X-ray diffraction studies.

Unusual reactions of a cationic carbyne complex of manganese with carbonyliron dianions to form a novel dimetal carbene-bridged complex [MnFe{µ-C(COEt)Ph}(η-C5H5)(CO)5

The reaction of [Mn(CPh)(η-C5H5)(CO)2]BBr41 with [NEt4]2[Fe2(CO)8] in tetrahydrofuran at low temperature gave a novel heteronuclear dimetal carbene-bridged complex [MnFe{µ-C(COEt)Ph}(η-C5H5)(CO)5]3, and a dimetal dicarbene complex [{(OC)2(η-C5H5)Mn(CPh)}2Fe2(CO)8]4, as well as [Mn(η-C5H5)-(CO)3]2. The same products, 2 and 3, were obtained from the reaction of 1 with Na2[Fe(CO)4]. The structure of 3 has been established by X-ray crystallography.

Carbohydratocarbene Complexes of Manganese and Rhenium

AbstractThe cationic carbyne complexes [Cp(CO)2MCR]+ [BX4]− [M = Mn, X = F: R = Ph (1), Tol (2); M = Re, X = 3,5‐C6H2(CF3)2: R = Ph (3)] add the anion of monodeprotonated protected mannofuranose (4a), glucofuranose (4b), and fructopyranose (4c) to the carbyne carbon atom to form the carbohydratocarbene complexes 5a–c, 6a, b, and 7a. With 5b, 5c, and 6b the addition proceeds with retention of configuration at the anomeric center. Due to inversion of configuration in the deprotonation step the complexes 5a, 6a, and 7a are obtained as β‐glycosides. The carbene ligand is oxidatively cleaved from the metal by trimethylamine N‐oxide or air. Cleavage of the C(carbene)O bond with reformation of the cation of the carbyne complex 2 is achieved by reaction of 6a with BCl3. Photolysis of [Cp(CO)2MnC(Ph)OEt] in the presence of L affords the carbene complexes [Cp(CO)(L)MnC(Ph)OEt] [L = P(OMe)3 (11), P(Tol)3 (12)]. Ethoxide abstraction from 11 and 12 by BF3 gives the chiral cationic carbyne complexes [Cp(CO)(L)MnCPh]+[EF4]− (13, 14) which add 4a to form the corresponding mannofura‐nosylcarbene complexes (15, 16). When 0.5 equivalents of 4a are employed in the reaction with 13, 14 the ratio of diastereomers is 3:2, both for 15 and 16. Complex 11 was characterized by an X‐ray structural analysis.

Addition, Cycloaddition, and Metathesis Reactions of the Cationic Carbyne Complexes [Cp(CO)2Mn.tplbond.CCH2R]+ and Neutral Vinylidene Complexes Cp(CO)2M:C:C(H)R (M = Mn, Re)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAddition, Cycloaddition, and Metathesis Reactions of the Cationic Carbyne Complexes [Cp(CO)2Mn.tplbond.CCH2R]+ and Neutral Vinylidene Complexes Cp(CO)2M:C:C(H)R (M = Mn, Re)Michael R. Terry, Lisa A. Mercando, Colleen Kelley, Gregory L. Geoffroy, Paul Nombel, Noel Lugan, Rene Mathieu, Robert L. Ostrander, Beth E. Owens-Waltermire, and Arnold L. RheingoldCite this: Organometallics 1994, 13, 3, 843–865Publication Date (Print):March 1, 1994Publication History Published online1 May 2002Published inissue 1 March 1994https://doi.org/10.1021/om00015a019RIGHTS & PERMISSIONSArticle Views333Altmetric-Citations60LEARN 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 (5 MB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Synthesis of µ-carbene and µ-carbyne complexes of rhodium and cobalt from substituted diazirines. Crystal structures of [Rh2(η5-C5Me5)2(CO)2{µ-C(C6H4F-4)(OMe)}] and [Rh2(η5-C5Me5)2(µ-CO)(µ-C6H4Me-4)][BPh4

The reaction of aryl(methoxy)diazirines with [M2(η5-C5Me5)2(µ-CO)2](M = Rh or Co) affords the µ-carbene complexes [M2(η5-C5Me5)(CO)2{µ-CR(OMe)}](R = aryl) in excellent yield. The carbonyl groups are terminal in the rhodium complexes, as demonstrated conclusively in an X-ray diffraction study, but bridging for the cobalt complex. Thermolysis of the rhodium complexes results in loss of CO and the formation of [Rh2(η5-C5Me5)2(µ-CO){µ-CR(OMe)}]. Protonation of either the mono- or di-carbonyl rhodium complex with HBF4 led to the formation of a stable cationic carbyne complex, [Rh2(η5-C5Me5)2(µ-CO)(µ-CR)][BF4]; the structure of the related [BPh4]– salt was established in a diffraction study. Dynamic processes in the complexes were investigated by variable-temperature NMR spectroscopy.

ChemInform Abstract: Transition-Metal Carbyne Complexes. Part 96. First Carbonyl-Free, Neutral and Cationic Phenylcarbyne Complexes of Tungsten with Isonitrile Ligands.

The neutral and cationic carbyne complexes (V) and (VI) are synthesized as shown in the scheme.

Übergangsmetal-Carbin-Komplexe: XCVI. Erste carbonylfreie, neutrale und kationische Phenylcarbin-Komplex von Wolfram mit Isonitril-Liganden

We have developed a largescale, stepwise procedure in which t-BuNC is used to transform trans-I(CO) 4WCC 6H 5 (I) into carbonyl-free, neutral and cationic tungsten phenylcarbyne complexes in good yields. The first step includes the replacement of two CO ligands in I by γ-picolin (pic) to give I(CO) 2(pic) 2WCC 6H 5 (II). II is then quantitatively converted into I(CO) 2(t-BuNC) 2WCC 6H 5 (III) with t-BuNC in refluxing CH 2Cl 2. More forcing conditions (toluene, 90°C) are necessary to replace the last two CO ligands in III by t-BuNC to give trans-I(t-BuNC) 4WCC 6H 5 (IV), which was isolated as a red crystalline solid in an overall yield of 65%. In the presence of t-BuNC in CH 2Cl 2 an equilibrium, which is established between IV and the cationic carbyne complex [(t-BuNC) 5WCC 6H 5] +I − (V), is shifted towards V by an excess of t-BuNC. This permits isolation of V as a brown solid at low temperature. V is unstable in THF, toluene and Et 2O at r.t., decomposing to IV and t-BuNC. In contrast the analogous PF 6-salt [(t-BuNC) 5WCC 6H 5] +(PF 6) − (VI), prepared from IV, t-BuNC and TlPF 6 in acetone, is stable in all solvents at r.t. The iodide ligand in IV is readily replaced by cyanide to yield trans-NC(t-BuNC) 4WCC 6H 5 (VII). The composition and structure of the new complexes II–VII have been determined by elemental analyses, IR, 1H NMR, 13C NMR spectroscopy and mass spectrometry.

Ein neuer Weg zu cyclopentadienyl-substituierten Diethylaminocarbin-Komplexen des Wolframs / A New Route to Cyclopentadienyl-Substituted Diethylaminocarbyne Complexes of Tungsten

We have developed a new, large scale, high yield synthesis of cyclopentadienyl-substituted tungsten diethylaminocarbyne complexes. In the first step an almost quantitative conversion of (η5-C5H5)W(CO)3I (1) and (η5-C5Me5)W(CO)3I (2) using EtNC and Me3NO occurs to give an isomeric mixture of cis and trans (η5-C5H5)W(CO)2(EtNC)I (3 a, 3b) and cis and trans (η5-C5Me5)W(CO)2(EtNC)I (4a, 4b), respectively. The isomeric mixtures of 3a and 3b and 4a and 4b are then quantitatively transformed with sodium powder in THF into the highly reactive, anionic isocyanide complexes Na[η(5-C5H5)W(CO)2(EtNC)] (5) and Na[(η5-C5Me5)W(CO)2(EtNC)] (6). Finally, alkylation of the strong nucleophiles 5 and 6 with Et3OBF4 occurs on the isocyanide nitrogen and yields the low-valent tungsten diethylaminocarbyne complexes (η5-C5H5)(CO)2W≡CNEt2 (7) and (η5-C5Me5)(CO)2W≡CNEt2 (8). Oxidative decarbonylation of 7 and 8 with iodine in CH2C12 gives the high-valent tungsten compounds (η5-C5H5)(I)2(CO)W≡CNEt2 (9) and (η5-C5Me5)(I)2(CO)W≡CNEt2 (10). 9 and 10 are subsequently converted with one equivalent of EtNC and TlPF6 into the cationic carbyne complexes [(η5-C5H5)(I)(EtNC)(CO)W≡CNEt2]PF6 (11) and [(η5-C5Me5)(I)(EtNC)(CO)W≡CNEt2]PF6 (12). Advantages of this route to low- and high-valent tungsten diethylaminocarbyne complexes are discussed in comparison to the classical Fischer procedure using the carbyne complex trans-I(CO)4W≡CNEt2 as precursor.

Cyclopentadienyl substituted diethylaminocarbyne complexes of tungsten in a higher oxidation state

The reaction of an equimolar mixture of (η 5-C 5H 5)(I) 2(CO)WCNEt 2 ( 1) and t-C 4H 9NC in THF at 50°C, results in the replacement of the CO ligand by isocyanide and formation of (η 5-C 5H 5)(I) 2( t-C 4H 9NC)WCNEt 2 ( 2). Complex 2 reacts further with t-C 4H 9NC in refluxing THF with displacement of the iodide ligand from the coordination sphere to give the cationic carbyne complex [(η 5-C 5H 5)(I)( t-C 4H 9NC) 2WCNEt 2] +I − ( 3). A new route to 2 in three steps has also been developed. The starting material, mer-I( t-C 4H 9NC) 3WCNEt 2 ( 4), is transformed with KC 5H 5 in refluxing THF to (η 5-C 5H 5)( t-C 4H 9NC)(CO)WECNEt 2 ( 5). Complex 5 is then oxidized with elemental iodine in CH 2Cl 2 to give [(η 5-C 5H 5)(I)( t-C 4H 9NC)(CO)WCNEt 2] +I − ( 6), the first cationic, carbonyl-containing carbyne complex of tungsten in a higher oxidation state. Finally, 6 is decarbonylated thermally in boiling THF to 20. The composition and structure of the new complexes 2, 3, 5 and 6 have been determined by total elemental analyses and IR, 1H NMR, 13C NMR spectroscopies, as well as by mass spectrometry. The non-ionic nature of 2 and ionic nature of 6 in solution, have been confirmed by conductivity measurements.

Preparation and structure of an unusually stable cationic µ-carbyne complex of rhodium

The reaction of either [(η5-C5Me5)2Rh2(CO)2{µ-C(OMe)Ar}] or [(η5-C5Me5)2Rh2(µ-CO){µ-C(OMe)Ar}] with H[BF4]·OEt2 yields the stable cationic carbyne complex [(η5-C5Me5)2Rh2(µ-CO)(µ-CAr)][BF4]; the structure of the complex for which Ar = 4-MeC6H4, with a [BPh4] counterion, was established in an X-ray diffraction study.

Übergangsmetall-Carbin-Komplexe, XC. Synthese neuer, siebenfach-koordinierter, kationischer Carbin-Komplexe des Wolframs in einer höheren Oxidationszahl / Transition Metal Carbyne Complexes, XC. Synthesis of New, Seven Coordinated, Cationic Tungsten Carbyne Complexes in a Higher Oxidation State

The reaction of (I)3(CO)L2W≡CNEt2 (L2 = 2.2'-bipyridyl(2.2'-bipy); 1.10-phenanthroline (ophen)) (1, 2) with two equivalents of tert-butylisonitrile results in the elimination of the carbonyl group and the displacement of one iodine ligand from the coordination sphere, leading to the new, cationic carbyne complexes [(I)2(t-C4H9NC)2L2W≡CNEt2]+I- (3, 4). The ionic character and composition of 3 and 4 was confirmed by the electrical conductivity of their solutions as well as by elemental analyses, IR, 1H NMR and 13C NMR spectroscopy.

Übergangsmetall-carbin-komplexe: XCI. Synthese isonitril-substituierter, neutraler und kationaischer diethylaminocarbin-komplexe des wolframs in niedriger und mittlerer oxidationszahl

The pyridine ligands in cis-I(CO) 2(py) 2CNEt 2 (I) can be readily replaced by CH 3NC or t-C 4H 9NC to yield the stable, neutral carbyne complxes cis-I(CO) 2(RNC) 2WCNEt 2 (R = CH 3 (II), t-C 4H 9 (III0). Upon oxidative decarbonylation with iodine, II and III are quantitatively transformed to the reactive to the reactive seven-coordinated carbonyl-containing carbyne complexes (I) 3(CO)(RNC) 2WCNEt 2 (R = CH 3(IV), t-C 4H 9 (V)) with tungsten in a higher oxidation state. Compounds IV and V react with an excess of RNC (R = CH 3, t-C 4H 9) upon elimination of the CO ligand and displacement of one iodine ligand from the coordination sphere to form the seven-coordinated cationic carbyne complexes [(I) 2(RNC) 4WCNEt 2] +I − R = CH 3 (VI), t-C 4H 9 (VII). The composition and structure of the new compounds were determined by elemental analyses and by IR, 1H NMR, and 13C NMR spectroscopy.

Übergangsmetall—Carbin-Komplexe: LXXXIX. Ein neuer Weg zu kationischen Carbin-Komplexen durch reduktive Eliminierung zweier Halogen-Liganden aus neutralen Diethylaminocarbin-Komplexen des Wolframs in einer hohen Oxidationszahl mit PMe 3

Upon oxidative decarbonylation with iodine, trans-I(CO) 2L 2WCNEt 2 complexes (L 2 = 2,2′-bipyridyl (2,2′-bipy); 1,10-phenanthroline (ophen)) (I, II) are quantitatively transformed to the seven-coordinated, carbonyl-containing carbyne complexes (I) 3(CO)L 2WCNEt 2 (L 2 = 2,2′-bipy, ophen) (III, IV) with tungsten in a high oxidation state. Complexes III and IV react with excess PMe 3 with reductive elimination of PMe 3I +I − to yield the cationic carbyne complexes [(PMe 3) 2(CO)-L 2WCNEt 2] +I − (V, VI).

Übergangsmetall-Carbin-Komplexe: LXXXVII. Synthese neuer, thermisch stabiler, kationischer Diethylaminocarbin-Komplexes des wolframs

trans-I(CO) 2L 2WCNEt 2 complexes (L 2  2,2′-bipyridyl (2,2′-bipy); 1,10-phenanthroline (ophen)) react with PR 3 (R  Me, Et) and thus undergo substitution of the iodine ligand by the phosphine to yield the new, thermostable, cationic carbyne complexes, [(PR 3)(CO) 2L 2WCNEt 2] + I −. The ionic character of the compounds has been established from electrical conductivity studies of their solutions. Spectroscopic investigations of the complexes, whose composition has been determined by elemental analysis, indicate that in this reaction the halogen ligand in the trans position has been displaced by the chelate ligand, while the phosphine ligand occupies a cis coordination site, relative to carbyne moiety.

An α-diazoalkylosmium complex as carbyne-complex precursor. Synthesis and X-ray crystal structure of [OsCl(I)(NO)(PPh2C6H4CHCO2Et)(PPh3)], the product of an intramolecular carbyne insertion reaction

The α-diazoalkylosmium complex [OsCl(I)(NO)(CN2CO2Et)(PPh3)2] loses N2 to give the title complex and the formation of this metallacyclic compound, which has been structurally cahracterised by single crystal X-ray diffraction, is interpreted as arising from an intramolecular insertion reaction of an intermediate cationic carbyne complex, [OsCl(NO)(C–CO2Et)(PPh3)2]I.

Übergangsmetall-Carben-Komplexe, CXXXI. Umsetzung von [(CO)5WCNEt2]BF4 mit anionischen Organylverbindungen von Elementen der V. Hauptgruppe/ Transition Metal Carbene Complexes, CXXXI. Reaction of [(CO)sWCNEt2]BF4 with Anionic Organyl Compounds of Group V Elements

Abstract The cationic carbyne complex [(CO)5WCNEt2]BF4 (1) reacts with potassiumdiphenylamide, KNPh2, with nucleophilic addition of the amide anion to give (CO)5W[C(NEt2)NPh2] (2). The corresponding reactions with KPPh2, KPEt2, KPMePh, NaSbPh2 and NaBiPh2 yield the complex [(CO)5W(CNEt2)]2 (3), which is formed by reductive dimerization of two carbyne fragments. In case of KPMePh the carbene complexes (CO)5W[C(NEt2)PMePh (4) and trans-(MePhPH)(CO)4W[C(NEt2)PMePh] (5) are also obtained. On warming in solution 5 spontaneously rearranges to the novel cyclic carbene complex (6). Reaction conditions, properties and spectroscopic data of the new compounds are reported.

Übergangsmetall-Carben-Komplexe, CXXVI [1]. Darstellung und Struktur symmetrischer Hydroxycarben-Anhydrid-Komplexe des Mangans und Rheniums / Transition Metal Carbene Complexes, CXXVI [1]. Preparation and Structure of Symmetrica! Hydroxycarbene Anhydride Complexes of Manganese and Rhenium

Abstract Symmetrical anhydrides of hydroxycarbene complexes of manganese and rhenium, [π-C5H5(CO)2MC(R)]2O, (M = Mn, Re) are prepared by reaction of cationic carbyne complexes [π-C5H5(CO)2MCR]BX4 with the corresponding metal carbonyl acylates Li[π-C5H5(CO)2MC(O)R]. [π-C5H5(CO)2MnC(C6H5)]2O is also obtained by controlled hydrolysis of π-C5H5(CO)2MnCX(Br)Ce6H5. The new complexes are characterized spectroscopically and by an X-ray structure analysis of [π-C5H5(CO)2MnC(C6H5)2O.

CαCα‐Coupling of Two {(CO)5CrCNEt2} Fragments by Reductive Dimerization of a Cationic Carbyne Complex

AbstractThe complete manuscript of this communication appears in: Angew. Chem. Suppl. 1982, 1036. DOI:10.1002/anie.198210360