Manganese Carbonyl Complexes Research Articles

Manganese Carbonyl Complexes as Catalysts for the Hydrosilation of Ketones: Comparison with RhCl(PPh3)3

Manganese carbonyl complexes catalyze the hydrosilation of ketones with PhMe2SiH and Ph2SiH2 in C6D6 solutions. Efficacy of the manganese carbonyl precatalysts (2.4 mol %) toward acetone hydrosilation with 1.1 equiv of PhMe2SiH to give (CH3)2CH(OSiMe2Ph) (3) varied: (PPh3)(CO)4MnC(O)CH3 (1) ( (CO)5MnC(O)CH3 > (CO)5MnCH3 > (CO)5MnBr (6.0 h) ≫ Mn2(CO)10 ≈ (PPh3)(CO)4MnBr ≈ (CO)5MnSiMe2Ph (2). A turnover frequency of 27 min-1 was measured for catalysis using 1% 1; rapid catalysis was possible with 0.1% 1 in the absence of solvent. As a precatalyst, 1 is much more reactive than Rh(PPh3)3Cl for the PhMe2SiH hydrosilation of acetone, acetophenone, and cyclohexanone; both catalysts exhibit similar reactivity with Ph2SiH2. With 1 as the precatalyst, isolated yields of the alkoxydimethylphenylsilanes exceeded 90%, with no evidence of competing dehydrogenative silation to yield vinyl silyl ethers. Photochemical activation of (CO)5MnSiMe2Ph (2) affords moderate hydrosilation catalytic activ...

Preparation and structures of tetrameric and dimeric manganese carbonyl complexes incorporating thiosalicylato ligands

Orthomanganated N, N-dimethylbenzamide reacts with SO 2 to give a tetra-manganese complex Mn 4(thsa) 2(CO) 16 (thsa = thiosalicylate = 2-thiobenzoate di-anion) which an X-ray structure determination shows to contain four Mn(CO) 4 units linked by two triply bridging (S,O,O) thsa ligands. Another product identified after aerobic work-up was the disulphide [2-( −OOC)C 6H 4S-] 2. Reaction of thiosalicylic acid with BrMn(CO) 5 in the presence of Et 3N gave good yields of [Et 3NH] 2[Mn 2(thsa) 2(CO) 6], the anion of which contains two [Mn( η 2-thsa)(CO) 3] − units doubly-linked via the S atoms.

The reduction and oxidation of cationic carbonyl complexes of manganese with phosphoniodithioformate: X-ray crystal structure of [Mn(CO) 4(S 2CPCy 3)]ClO 4

Manganese carbonyl complexes of the types behaviour have been studied by cyclic voltammetry and controlled potential electrolysis, showing that they undergo one-electron reduction and one-electron oxidation at potentials that depend mainly on the number of carbonyls. The results have been explained on the basis on an MO study at an EH level carried out on the model complexes [Mn(CO) 4(S 2CPH 3)] + ( 1b), fac-[Mn(CO) 3PH 3(S 2CPH 3)] + ( 2d), cis,trans-[Mn(CO) 2(PH 3) 2(S 2CPH 3)] + ( 3d), mer-[Mn(CO) 3PH 3(S 2CPH 3)] + ( 4), trans,cis-[Mn(CO) 2(PH 3) 2(S 2CPH 3)] + ( 5), and cis,cis-[Mn(CO) 2(PH 3) 2(S 2CPH 3)] + ( 6).

Organometallic photochemistry in supercritical fluids: Reactions of cyclopentadienyl carbonyl and phosphine carbonyl complexes of manganese with dinitrogen

UV photolysis has been used to generate dinitrogen compounds by substitution of CO groups by N 2 in supercritical fluid solvents (scXe, scCO 2 and scC 2H 6) containing high pressures of N 2. Compounds include Cp'Mn(CO) 2L (Cp′  C 5H 4Me; L  PMe 3- x Ph x , x = 0 to 3). A semi-quantitative comparison of the photolysis of Cp★Mn(CO) 3 (Cp★  C 5Me 5) and N 2 in ScXe and scCO 2 indicates that there is little difference between the effectiveness of the photolysis in these two supercritical solvents. The Timney Ligand Effect approach is used to rationalise the fact that some of the ν(CO) and ν(NN) bands of Cp★Mn(CO) 2(N 2) and Cp★Mn(CO)(N 2) 2 are nearly coincident.

Photo-, electro-, and thermal carbonylation of alkyl iodides in the presence of group 7 and 8–10 metal carbonyl catalysts

Various transition-metal complexes including Group 7 and 8–10 metal carbonyls are highly active catalyst precursors for the photochemical carbonylation of alkyl iodides having β-hydrogens on saturated sp 3-carbons at room temperature under 1 atm of carbon monoxide. Primary, secondary and tertiary alkyl iodides are smoothly carbonylated by this catalyst system without β-hydride elimination (dehydrohalogenation) to give the corresponding esters or amides in high yields. In employment of Mn 2(CO) 10 as a catalyst, electrochemical carbonylation of alkyl iodides also occurred via generation of an anionic manganese carbonyl intermediate. Actually, anionic manganese carbonyl complexes (pentacarbonylmanganates) showed high catalytic activity for thermal carbonylation of alkyl iodides at room temperature under 1 atm of carbon monoxide without photo-irradiation and electrolysis. Mechanistic studies were performed with kinetics and ESR and it was suggested that the present photo-, electro- and thermal carbonylation would involve a non-chain radical mechanism.

Manganese Carbonyl Bromide-Catalyzed Alcoholysis of the Monohydrosilane HSiMe2Ph

The dimeric manganese carbonyl bromide [Mn(CO)[sub 4]Br][sub 2] is an effective catalyst for the alcoholysis of dimethylphenylsilane in benzene at room temperature. Preparative scale procedures using a 1200:1200:1 mixture of alcohol, HSiMe[sub 2]Ph, and [Mn(CO)[sub 4]Br][sub 2] (0.084 mol%) afforded samples of analytically pure alkoxysilanes in good yields. tert-Butyl alcohol, for example, gave (CH[sub 3])[sub 3]COSiMe[sub 2]Ph in 82% yield after a 35-min reaction time, and allyl and propargyl alcohols quantitatively transformed to their alkoxysilane derivatives, with no evidence of competing hydrosilation of the carbon-carbon multiple bonds. Competitive reactions involving 1:1:1 mixtures of 2-butanol-acetone-HSiMe[sub 2]Ph and [Mn(CO)[sub 4]Br][sub 2] as catalyst exhibited chemoselective alcoholysis of dimethyl-phenylsilane. [sup 1]H NMR spectral monitoring of catalyzed reactions between methanol or 2-butanol and HSiMe[sub 2]Ph was used in screening other manganese carbonyl complexes as potential HSiMe[sub 2]Ph alcoholysis catalysts. Their reaction times varied as follows: [Mn(CO)[sub 4]Br][sub 2] > Mn(CO)[sub 5]Br [much gt] Mn(CO)[sub 5]CH[sub 3] [approx] Mn(CO)[sub 5]C(O)Ph > Mn(PPh[sub 3])(CO)[sub 4]Br > Mn(PPh[sub 3])(CO)[sub 4]C(O)CH[sub 3] [much gt] Mn(CO)[sub 5](SiMe[sub 2]Ph) [much gt] Mn[sub 2](CO)[sub 10] [approx] Rh(PPh[sub 3])[sub 3]Cl (no reaction). Solvent-dependent turnover frequencies were determined for the [Mn(CO)[sub 4]Br][sub 2]-catalyzed dehydrocoupling of 2-butanol and HSiMe[sub 2]Ph for 0.289 M solutionsmore » of 2-butanol and HSiMe[sub 2]-Ph with 1.4 mol% precatalyst [Mn(CO)[sub 4]Br][sub 2]. 29 refs., 5 tabs.« less

Reactions of unsaturated dihydrido carbonyl complexes of manganese(I) with nitriles and isonitriles. Preparation and characterization of the first binuclear .mu.,.eta.1,.eta.2-NCR derivatives

Reactions of unsaturated dihydrido carbonyl complexes of manganese(I) with nitriles and isonitriles. Preparation and characterization of the first binuclear .mu.,.eta.1,.eta.2-NCR derivatives

ChemInform Abstract: The Stereospecific Synthesis of Mono‐ and Binuclear (Ligand‐Bridged) Carbonyl Complexes of Manganese: A Review

ChemInformVolume 21, Issue 50 Reviews ChemInform Abstract: The Stereospecific Synthesis of Mono- and Binuclear (Ligand-Bridged) Carbonyl Complexes of Manganese: A Review G. A. CARRIEDO, Dep. Quim. Organomet., Univ. Oviedo, 33071 Oviedo, SpainSearch for more papers by this authorV. RIERA, Dep. Quim. Organomet., Univ. Oviedo, 33071 Oviedo, SpainSearch for more papers by this author G. A. CARRIEDO, Dep. Quim. Organomet., Univ. Oviedo, 33071 Oviedo, SpainSearch for more papers by this authorV. RIERA, Dep. Quim. Organomet., Univ. Oviedo, 33071 Oviedo, SpainSearch for more papers by this author First published: December 11, 1990 https://doi.org/10.1002/chin.199050359Read 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. Volume21, Issue50December 11, 1990 RelatedInformation

Synthesis of new carbonyl complexes of manganese(I) containing monodentate Ph2PCH2PPh2 (dppm)

The complex fac-[Mn(CO)3(bipy)(PP′)]A [PP′ = monodentate Ph2PCH2PPh2 (dppm), A = ClO4- or PF6-] reacts with ONMe3 in CH2Cl2 to give cis-[Mn(CO)2(bipy)(PP)]A, and with dppm in refluxing acetone, to give cis,trans-[Mn(CO)2(bipy)(PP′)2]A. Irradiation with UV light of the latter gives the monocarbonyl mer-[Mn(CO)(bipy)(PP)(PP′)]A, containing one chelated and one monoden-tated dppm. Although the fac-[Mn(CO)3(bipy)(PP′)]PF6, reacted with fac-[MnBr(CO)3(bipy)] and TIPF6, to give the binuclear bridged species {[Mn(CO)3(bipy)]2(μ-PP)}(PF6)2, attempts to use the complexes with monodentated dppm as ligands to form compounds of higher nuclearity resulted in splitting of the dppm bridges.

Isocyanide migration from an axial to an equatorial position in the synthesis of octahedral cationic carbonyl complexes of manganese(I) containing nitrogen donor chelate ligands

Several manganese carbonyl complexes of the type [Mn(CO) m (CN tBu) n (L) p (LL)]ClO 4 ( m + n + p = 4; m = 1−3; n = 1−3; p = 0, 1; L = P(OMe) 3, CNPh; LL = 2,2′-bipiridine (bipy), 1,10-phenantroline (phen), bis(t-butyl)-1,4-diazabuta-2,3-diene ( tBu-DAB), N,N,N′,N′-tetramethylethylendiamine (tmed)) have been prepared starting either from fac-[Mn(CO) 3(CN tBu)(LL)]ClO 4 or fac-[Mn(CO) 3{P-(OMe) 3}(LL)]ClO 4 and using ONMe 3 as decarbonylating agent. The stereochemistry of the substitution reactions products is discussed in terms of the nature of the possible intermediates.

The stereospecific synthesis of mono- and bi-nuclear (ligand-bridged) carbonyl complexes of manganese: a review

A review is given of the routes that can be used to give the different isomeric forms of mono- and bi-nuclear manganese carbonyl complexes of the general types [Mn(CO) 4− n ( L L )L n ] + and [L n ( L L )(CO) 3− n Mn-X-Mn(CO) 3− m ( L L )′ L′ m ] +, where L L are chelating bidentate ligands and X is a bridging ligand.

Synthesis of bimetallic carbonyl complexes of manganese, rhodium, and ruthenium from 1,4-bis(cyclopentadienylthallium)-1,4-butadione

1,4-Bis(cyclopentadienylsodium)-1,4-butadione was prepared from reaction of sodium cyclopentadienide and diethylsuccinate and converted into its thallium analog by metal exchange using thallium ethoxide. Reaction of the thallium reagent with BrMn(CO) 5 yielded 1,4-bis(cymantrenyl)-1,4-butadione, while reaction with [ClRh(CO) 2] 2 gave both a bis(cyclopentadienylrhodiumdicarbonyl) complex and a small amount of a bis(cyclopentadienylrhodiumcarbonyl)-μ-carbonyl species. This latter material was found to undergo slow exchange on the NMR time scale which is believed to involve a side-to-side movement of both the μ-carbonyl and interring bridge. A complete variable temperature analysis of this motion was carried out. Reaction of the thallium reagent with [Cl 2Ru(CO) 3] 2 resulted in the formation of a bis(cyclopentadienylrutheniumdicarbonyl) complex and small quantities of two other materials which have not yet been characterized. With the exception of these last two, all transition metal compounds have been fully characterized with Ir, 1H and 13C NMR, mass spectroscopy and elemental analysis.

Manganese complexes with S2CPEt3 ligands. X-Ray crystal structures of cis-trans-[Mn(CO)2(PEt3)2(S2CPEt3)]ClO4 and cis-trans-[Mn(CO)2(PEt3)2(S2CH)

A variety of manganese(I) carbonyl complexes containing triethylphosphine and monodentate or chelate triethylphosphoniodithiocarboxylato ligands can be obtained by substitution reactions either under mild conditions or by thermal or photochemical methods. The products resulting from the thermal reactions between bromo carbonyls and S2CPEt3 are very different from those obtained with S2CP(C6H11)3 under similar conditions, and this can be attributed to the difference in electronic and steric properties of the phosphines concerned. The X-ray structure of cis,trans-[Mn(CO)2(PEt3)2(S2CPEt3)]ClO4 has been determined. Reduction of this compound with NaBH4 affords the neutral dithioformate complex cis,trans-[Mn(CO)2(PEt3)2(S2CH)] which has been characterized by spectroscopic methods and by X-ray crystallography.

Photochemistry of some manganese and chromium dinuclear metal carbonyl complexes in frozen gas matrices at ca. 12 K

Infrared spectroscopic evidence is presented to show that photolysis of the non-metal–metal bonded dimers [Mn2(µ-η5:η5′-C10H8)(CO)6], [Mn2(µ-η5:η5′-C5H4CH2C5H4)(CO)6], [Cr2(µ-η6:η6′-C12H10)(CO)6], and [Cr2(µ-η6:η6′-C14H14)(CO)6] together with its mononuclear analogue [Cr(η6-C7H8)(CO)3] in gas matrices at ca. 12 K results in CO ejection to yield [M(CO)2] molecular fragments rather than detachment of polyene rings or the formation of new M–M linkages via M–M bonding and/or CO bridging. The reactivity of the resultant [M(CO)2] molecular fragments is demonstrated by the recombination with CO when matrices (Ar, CH4) were irradiated with light of a longer wavelength and by the reactions with N2 and 13CO (5% in Ar or CH4) to afford [M(CO)2(N2)] and [M(12CO)n(13CO)3 –n] fragments, respectively. The failure to form new M–M linkages is attributed to the isolation of the dimers in pseudo-trans configurations in the matrix cages such that even the excess photochemical energy is insufficient to both cleave M–CO bonds and supply the energies required to rotate the bulky fragments in the rigid matrix cages. These findings are discussed in relation to solution photochemical reactions.

Reactions of an imidoyl halide with manganese carbonyl complexes

PhC(=NPh)Cl has been allowed to react with both [Mn(CO) 5] − and Mn 2(CO) 10. The carbonylate anion gave (CO) 4M n[C(H)(C 6H 5)N(C 6H 5)C(C 6H 5)=N (C 6H 5)] which results from head-to-tail coupling of two imidoyl groups and reduction of the internal C=N bond. This compound has been characterized by X-ray crystallography. With Mn 2(CO) 10 the diazabutadiene complex [(C 6H 5)N=C(C 6H 5)C(C 6H 5)=N(C 6H 5)]Mn 2(CO) 6 was isolated.

Coupling of iminoacyl groups to diazabutadienes on manganese carbonyl complexes

Formation des complexes [p-MeC 6 H 4 N=C(R)C(R)=NC 6 H 4 p-Me]Mn 2 (CO) 6 a partir de RC(O)Mn(CO) 4 (CNC 6 H 4 pMe), R=p-ClC 6 H 4 CH 2 , C 6 H 5 CH 2 , p-MeOC 6 H 4 CH 2 . Etude radiocristallogaphique du complexe pour lequel R=p-ClC 6 H 4 CH 2

Ligand substitution in manganese(I) carbonyl complexes Mn(CO)5X (X = Cl, Br): activation parameters and x-ray structure of Mn(CO)3(dab)Cl (dab = biacetyl bis(phenylimine))

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLigand substitution in manganese(I) carbonyl complexes Mn(CO)5X (X = Cl, Br): activation parameters and x-ray structure of Mn(CO)3(dab)Cl (dab = biacetyl bis(phenylimine))G. Schmidt, H. Paulus, R. Van Eldik, and H. EliasCite this: Inorg. Chem. 1988, 27, 18, 3211–3214Publication Date (Print):September 1, 1988Publication History Published online1 May 2002Published inissue 1 September 1988https://doi.org/10.1021/ic00291a034RIGHTS & PERMISSIONSArticle Views284Altmetric-Citations24LEARN 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 (532 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Infrared spectroscopy of excited states and transients in photochemistry

Flash photolysis with time-resolved IR detection is used in investigations of the primary photoreactions of chromium, molybdenum, tungsten, manganese, iron, and osmium carbonyl complexes, and of the ensuing transformations of transient products in room temperature solution. The method bridges the gap to spectral data obtained at low temperatures. It provides information which has previously been inaccessible, such as detailed structural information, and kinetic data in cases where the UV-visible absorptions of the species of interest overlap. Finally, excited-state IR spectroscopy has now become feasible for many organic compounds with the most recent instrumental set-up which reaches a time resolution of ≥ 50 ns.

Neutral and cationic carbonyl complexes of manganese with tetramethylthiourea. Crystal structure of cis-{Mn(CO) 4(SC[N(CH 3) 2] 2) 2} CIO 4

Tetramethylthiourea (TMTU) reacts with Mn 2(CO) 10 in hexane under UV irradiation to give axial Mn 2(CO) 9(TMTU), with MnBr(CO) 5 in CH 2Cl 2 at room temperature to give cis-MnBr(CO) 4(TMTU), and with Mn(OClO 3(CO) 5 in CH 2Cl 2 to give the cationic tetracarbonyl cis-[Mn(CO) 4(TMTU) 2]CIO 4. The last complex has been characterized by X-ray diffraction; it reacts with more (TMTU) to give the unstable species fac-[Mn(CO) 3(TMTU) 3]ClO 4, with pyridine to give fac-[Mn(CO) 3(PY) 2(TMTU)]ClO 4, and with the bidentate ligands ▪ o-phenanthroline or bis-diphenylphosphinomethane to give the corresponding cationic fac-tricabonyls fac-[Mn(CO) 3 ▪(TMTU)]ClO 4. In all the complexes prepared the TMTU ligand is S-bonded to the manganese.

Carbonyl complexes of manganese(I) with pyridazine: Synthesis and1H n.m.r. study

Three new pyridazine complexes of manganese(I): [MnBr(pyr)2(CO)3] (1), [Mn(pyr)(CO)5][ClO4] (2) and [Mn(pyr)3(CO)3][ClO4] (3) (pyr=pyridazine) have been prepared and their i.r. and variable-temperature1H n.m.r. spectra investigated.