10170-69-1Relevant articles and documents
Manganese-Mediated C-C Bond Formation: Alkoxycarbonylation of Organoboranes
Van Putten, Robbert,Filonenko, Georgy A.,Krieger, Annika M.,Lutz, Martin,Pidko, Evgeny A.
, p. 674 - 681 (2021)
Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.
Preparation of Some Metallodithiocarboxylato- and Metallodithiocarbene-metal Complexes
Busetto, Luigi,Palazzi, Antonio,Monari, Magda
, p. 1631 - 1634 (1982)
The reaction between the carbon disulphide adduct of dicarbonyl(cyclopentadienyl)iron, (1+) (cp=η5-C5H5), and (M=Mn or Re) produces in good yield the heterodinuclear complexes in which the CS2 group acts as a bridge in the unit FeC(=S)SM.Depending on the reaction conditions, both the chelato-complex and the unidentate derivative are obtained.Alkylation of the thione sulphur atom in the unit FeC(=S)SRe produces the dithiocarbene (1+) in good yield.The reaction of this metallodithiocarbenemetal complex with methylamine yields and .The compounds and were formed from the reaction of (1+) with LiBr.
SYNTHESIS GAS INCORPORATION INTO ACYLMANGANESE PENTACARBONYLS
Sheeran, Daniel J.,Arenivar, John D.,Orchin, Milton
, p. 139 - 146 (1986)
The reaction of p-CH3C6H4(13)C(O)Mn(CO)5 with H2/CO at 2400 psi in hexane solvent leads to incorporation of 1/1 H2/CO and essentially exclusive production of the oxycarbonyl, p-CH3C6H4(13)CH2OC(O)Mn(CO)5.The success of this unusual reaction appears to depend on the dihaptocarbonyl nature of an intermediate acylmanganese tetracarbonyl as well as on the use of a hydrocarbon solvent.The reaction is quite general and has even been extended to acylmanganese compounds derived rom dibasic acids.In the initial stage of the reaction it seems likely that a carbenic intermediate arising from the dihapto structure is involved but attempts to trap such a species were unsuccessful.The possiblity that the reaction proceeds by initial hydrogenolysis of the acylmanganese compound to aldehyde and HMn(CO)5, followed by rection of these two species with each other to give product, has been ruled out.
Brimm, E. O.,Lynch, M. A.,Sesny, W. J.
, p. 3831 - 3835 (1954)
Synthetic, structural and reaction chemistry of transition metal complexes containing the mesitylborylene ligand
Coombs, Deborah L.,Aldridge, Simon,Jones, Cameron
, p. 3851 - 3858 (2002)
The synthesis, spectroscopic and structural characterization of the bromo-boryl complexes (η5-C5R4R′)Fe(CO)2- B(2,4,6-Me3C6H2)Br (R = R′ = H, 2; R = H, R′ = Me, 3; R = R′ = Me, 4) are reported. These are shown to be versatile substrates for the synthesis of both asymmetric boryl complexes [e.g. (η5-C5H5)Fe(CO)2B(2,4,6-Me 3C6H2)OC6H4 tBu-4, 6], and bridging borylene complexes {e.g. [η5-C5H4R)Fe(CO)2] 2B(2,4,6-Me3C6H2), R = H, 7; R = Me, 8} via substitution chemistry with retention of the metal-boron bond. Complexes 7 and 8 are thefirst reported examples of structurally characterized bridging borylene complexes without a supporting M-M bond. Photolytically induced CO loss from [η5-C5H5)Fe(CO)2] 2B(2,4,6-Me3C6H2) yields the complex [η5-C5H5)Fe(CO)]2(μ 2-CO)[μ2-B(2,4,6-Me3C6H 2)] (11), which features a supported bridging borylene ligand.
Manning, Mark C.,Trogler, William C.
, p. 247 - 250 (1981)
Electron and bromine transfer reactions between metal carbonyl anions and metal carbonyl bromides. Crystal and molecular structure of dimeric indenyl molybdenum tricarbonyl
Striejewske, William S.,See, Ronald F.,Churchill, Melvyn Rowen,Atwood, Jim D.
, p. 4413 - 4419 (1993)
Reactions of metal carbonyl anions with metal carbonyl halides proceed by two separate paths. When the reactant anion is a strong nucleophile, the halogen is transferred, resulting in a new metal carbonyl halide and a new metal carbonyl anion as intermediates. The ultimate products, in this case, are the homobimetallic complexes. In cases where the reactant metal carbonyl anion is a poor nucleophile, a single electron transfer occurs, leading to the two homobimetallic complexes and to the heterobimetallic complex. Halide effects and possible indenyl effects are examined. The complex [Mo(indenyl)(CO)3]2 crystallizes in the noncentrosymmetric orthorhombic space group P212121 (No. 19) with a = 7.3572(7) ?, b = 14.4539(12) ?, c = 19.983(2) ?, V = 2125.0(4) ?3, and Z = 4. Diffraction data were collected on a Siemens R3m/V diffractometer for 2θ = 5-45° (Mo Kα), and the structure was solved and refined to R = 3.21% and Rw = 3.23% for all 2786 independent reflections (R = 2.26% and Rw = 2.81% for those 2314 reflections with |Fo|> 6σ(|Fo|). The complex is held together by a Mo-Mo single bond (Mo(1)-Mo(2) = 3.251(1) ?), and has Mo-CO distances ranging from 1.956(6) to 1.988(7) ?, averaging 1.970 ± 0.016 A. Molybdenum-carbon distances to the η5-indenyl rings range from 2.300(7) to 2.427(6) ? for Mo(1) and 2.306(7) to 2.430(6) ? for Mo(2).
Inglis, Thomas,Kilner, Melvyn
, (1976)
Thermal and photolytic substitution of dimanganese decacarbonyl with trifluorophosphine
Grimm, Casey C.,Brotman, Paul E.,Clark, Ronald J.
, p. 1119 - 1123 (1990)
Under thermal conditions, the PF3 substitution of Mn2(CO)10 produces five different compounds: 1-Mn2(CO)9(PF3), 1,1′-Mn2(CO)8(PF3)2, 1,2-Mn2(CO)8(PF3)2, 1,1′,2-Mn2(CO)7(PF3)3, and 1,1′,2,2′-Mn2-(CO)6(PF3) 4. Photolytic excitation results in the formation of four additional compounds. Substitution is rigorously limited to the replacement of four carbon monoxides, but that replacement is fairly readily achieved. Compounds are identified by using a combination of GC-MS, 19F NMR, and IR. Back reaction of 1,1′,2,2′-Mn2(CO)6(PF3)4 with 13CO produces only the previously observed PF3-substituted compounds having extensive label. Side products produced include the monometallic hydride series HMn(CO)5-x(PF3)x (x = 1-5), the hydrogen-bridged series Mn2(μ-H)(μ-PF2) (CO)8-x(PF3)x (x = 2-5), and the bisphosphido-bridged series Mn2(μ-PF2)2(CO)8-x(PF 3)x (x = 2-7).
Hepp, Aloysius F.,Wrighton, Mark S.
, p. 5934 - 5935 (1983)
Seder, T. A.,Church, Stephen P.,Weitz, Eric
, p. 1084 - 1086 (1986)
Matrix infrared spectra and density functional calculations of manganese and rhenium carbonyl neutral and anion complexes
Andrews, Lester,Zhou, Mingfei,Wang, Xuefeng,Bauschlicher Jr., Charles W.
, p. 8887 - 8897 (2000)
The reaction of laser-ablated Mn and Re atoms and electrons with CO upon co-condensation in excess argon and neon generated the carbonyl neutral and anion complexes. These species were identified via density functional theory isotopic frequency calculatio
Synthesis, characterization, and thermochemistry of (η1-C13H9)MN(CO)5 and (η5-C13H9)MN(CO)3
Decken, Andreas,MacKay, Andrew J.,Brown, Martin J.,Bottomley, Frank
, p. 2006 - 2009 (2002)
Reaction of LiC13H9 with Mn(CO)5Br at -78 °C gave (η1-C13H9)Mn(CO)5, 2. Thermal rearrangement of 2 yielded (η5-C13H9)Mn(CO)3, 1, 9, 9′
Photoredox reaction of cobalticinium pentacarbonylmanganate(-I) induced by outer-sphere metal to metal charge transfer excitation
Kunkely, Horst,Vogler, Arnd
, p. C29 - C43 (1989)
The salts +- and +- show long-wavelength absorptions at λmax 749 nm and 665 nm.These bands are assigned to metal to metal charge transfer (MMCT) transitions from Mn-I to CoIII and CrI.Upon MMCT excitation the former ion pair is converted to Co(C5H5)2 and Mn2(CO)10.The latter ion pair undergoes an analogous redox reaction as a thermal process.The thermal and the light-induced electron transfer are explained on the basis of the Hush model.
REACTIONS OF BIS(η4-1,5-CYCLOOCTADIENE)NICKEL(0) WITH TRANSITION METAL HALIDES, AND THE CRYSTAL STRUCTURE OF μ-DICHLORO-BIS(TETRAHYDROFURAN)HEXACARBONYLDIMANGANESE
VanDerveer, Michael C.,Burlitch, James M.
, p. 357 - 368 (1980)
Bis-(η4-1,5-cyclooctadiene)nickel(0) reacted with η5-C5H5Fe(CO)2Cl, η3-C5H5Fe(CO)3Cl, Mn(CO)5Cl and (CO)4>2 to form metal-metal bonded coupling products.Partial reduction of Mn(CO)5Cl gave 2 shown to have a chlorine-bridged C2h structure by X-ray diffraction analysis.Ligand transfer also accompanied the reduction of Fe2(CO)2Br2 and Fe(CO)4Cl2 to Fe2(CO)3 and Fe(CO)5, respectively.Only partial reduction was observed for Ti(acac)2Cl2 and (η5-C5H5)2TiCl2 which gave 2 and (η5-C5H5)2Ti(py)Cl, respectively.
Laser Photolysis Study of the Photosubstitution in Dimanganese Decacarbonyl
Yesaka, Hiroshi,Kobayashi, Takayoshi,Yasufuku, Katsutoshi,Nagakura, Saburo
, p. 6249 - 6252 (1983)
Two primary photoprocesses in the flash photolysis of Mn(CO)10 are established with the use of a 10-ns N2 laser.One is the cleavage of the Mn-Mn bond to form .Mn(CO)5 radicals, and the other is the cleavage of the Mn-CO bond to form Mn(CO)9.The reactivity of Mn2(CO)9 toward ligands is found to decrease in the following order: P(n-Bu)3>>t-BuNC ca.EtCN>>CO.The substitution of CO in the .Mn(CO)5 radical with P(n-Bu)3 is shown to be associative.The reactivity of Mn2(CO)9 toward P(n-Bu)3 is higher than that of .Mn(CO)5.
Orthomanganated arenes in synthesis. 9. Photochemical reactions of alkynes with orthomanganated triphenyl phosphite
Grigsby, Warren J.,Main, Lyndsay,Nicholson, Brian K.
, p. 397 - 407 (1993)
The reaction of orthomanganated triphenyl phosphite, (PhO)2P(OC6H4)Mn(CO)4 (1), with alkynes (C2Ph2, C2(COOMe)2, PhCCH, Me3SiCCH) under UV irradiation gives products derived from insertion of the alkyne into the Mn-C bond. The main products are the seven-membered metallacyclic species (PhO)2P(OC6H4)C(R2)=C(R 1)Mn(CO)4 (2) (both regioisomers for the unsymmetrical alkynes). Also obtained from the C2Ph2 reaction was (PhO)2POC6H4)C(Ph)=C(Ph)C(O)Mn(CO)3 (4), formed by insertion of both C2Ph2 and CO, and a compound {2,6-[PhCH=C(Ph)]2C6H3O}{2-[PhCH=C(Ph)]C 6H4O}POC6H4)Mn(CO)4 (3) derived from 1 by substitution with -C(Ph)=C(Ph)H groups at three of the ortho sites on the unmetalated phenoxy rings by a sequence of insertion/demetalation steps. A metal acetylide, PhCCMn(CO)3[P(OPh)3]2 (6) was also isolated from the reaction with PhCCH. Crystal structures are described for 2e (R1 = Ph, R2 = H; triclinic, space group P1, a = 10.619 (11) ?, b = 10.896 (6) ?, c = 11.619 (8) ?, α = 77.68 (5)°, β = 80.81 (7)°, γ = 80.31 (6)°, Z = 2, 2772 reflections, R = 0.039), 3 (monoclinic, space group P21/n, a = 10.743 (6) ?, b = 27.456 (23) ?, c = 17.536 (14) ?, β = 104.86 (5)°, Z = 4, 3941 reflections, R = 0.0599), 4 (monoclinic, space group P21/n, a = 9.907 (6) ?, b = 18.458 (11) ?, c = 16.539 (8) ?, β = 94.35 (4)°, Z = 4, 2565 reflections, R = 0.104), and 6 (orthorhombic, space group P212121, a = 19.888 (6) ?, b = 19.732 (8) ?, c = 10.467 (4) ?, Z = 4, 3085 reflections, R = 0.0523).
Synthesis and Reactions of Titanoxycarbene-Metal Carbonyl Complexes
Mashima, Kazushi,Jyodoi, Kouki,Ohyoshi, Akira,Takaya, Hidemasa
, p. 2065 - 2076 (1991)
A family of titanoxycarbene-metal carbonyl complexes of formula Cp*2TiOC(=MLn)CH2CH2 (3), where Cp* = η5-C5Me5 and MLn = Cr(CO)5, Mo(CO)5, W(CO)5, Mn2(CO)9, and Re2(CO)9, has been prepared by the treatment of titanocene-ethylene complex 1 with metal carbonyls of group 6 and 7.Complex 3b crystallizes in space group P2/a (Z=8) with cell constants a=30.401(1), b=9.251(1), c=27.561(5) Angstroem, β=105.73 (1) deg, and V=7460(2) Angstroem3 (data taken at -40 deg C, 6715 reflections, R=0.069).Two independent molecules of 3b in crystal make an enantiomorphic pair.A notable feature of the structure is the long distance of Ti-O bond coupled with the short distance of C(2)-O bond, which is characterized by a large contribution of zwitterionic canonical form 7.Thermal decomposition of 3 affords ethylene and the corresponding metal carbonyls, indicating that the C(carbenic)-C(3) bond fission occurred selectively, which is rather unusual for conventional Fischer-type carbene complexes.Complexes 3 react rapidly with atmospheric pressure of carbon monoxide below -30 deg C to produce cyclic acyltitanium complexes 12.The reverse reactions occur even below -30 deg C upon replacement of carbon monoxide by argon.Complex 3b also reacts with t-butyl isocyanide with a cleavage of the Ti-O bond to give 1:2 adduct 17, whose molecular structure has been elucidated by X-ray crystallography 1/n with cell constants a=14.964(2), b=26.207(4), c=14.719(3) Angstroem, β=100.30(1) deg, and V=5679(2) Angstroem3 (measured at -120 deg C, 5311 reflections, R=0.068)>, revealing that it has a novel zwitterionic structure possessing (η2-imidoyl)titanium cation and anionic acyldirhenium carbonyl moieties linked by an ethylene bridge.The controlled experiments show that complex 16 in which acyl ligand is trans to the Re-Re bond is the precursor of complex 17.Complex 18, a tungsten analogue of 17, has also been prepared.Reactions of 3b and 3e with acetylenes are also described.
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Darst,Lukehart
, p. 219 (1978)
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Gibson, Dorothy H.,Hsu, Wen-Liang
, p. 93 - 100 (1982)
The synthesis of heteronuclear transition metal clusters derived from alkylidyne tricobalt cluster precursors. I. The reaction of (μ3-CCl)Co3(CO)9 with transition metal carbonyl anions. The crystal and molecular structure of (μ3-CCl)
Duffy, D. Neil,Kassis, Maram M.,Rae, A. David
, p. 97 - 104 (1993)
Metal exchange reactions were used to produce heterometallic clusters derived from alkylidyne tricobalt precursors. Reaction of the cluster (μ3-CCl)Co3(CO)9 with the potassium salt of (η5-C5H5)Mo(CO)3- produced (μ3/s
Mixed-valence manganese carbonyl complexes with supersilyl thiolate ligands: [(OC)4Mn(μ -SSitBu3)2Mn(THF)X] (X = Br, SSitBu3) and Na(THF)6[(OC)3Mn(μ-SSi/Bu 3)3MnSSitBu3]
Kueckmann, Theresa I.,Schoedel, Frauke,Saenger, Inge,Bolte, Michael,Wagner, Matthias,Lerner, Hans-Wolfram
, p. 3272 - 3278 (2008)
The manganese carbonyl thiolates [(OC)4Mn(μ-SSitBu 3)2Na(THF)2], [(OC)4Mn(μ- SSitBu3)2Mn(THF)Br], [(OC)4Mn(μ-SSitBu 3)2Mn(THF)SSitBu3], and Na(THF) 6[(OC)3Mn(μ-SSitBu3) 3MnSSitBu3] can be prepared from the precursors Na(THF)2SSitBu3 and [Mn(CO)5Br]. When [Mn(CO)5Br] is treated with 1 or 2 equiv of Na(THF) 2SSkBu3, the 1:2 substitution product [(OC) 4Mn(a-SSitBu3)2Na(THF)2] (monoclinic, P21/C) is formed quickly. When additional amounts of [Mn(CO)5Br] are present (as in the 1:1 reaction) or are subsequently added to the reaction mixture, the dinuclear Mn(I)Mn(II) complex [(OC) 4Mn(μ-SSitBu3)2Mn(THF)Br] (monoclinic, P21/n) can be obtained along with [Mn2(CO)10]. Treatment of [(OC)4Mn(μ-SSitBu3)2Mn(THF)Br] with 1 equiv of Na(THF)2SSitBu3 gives the mixed-valence dinuclear manganese thiolate complex [(OC)4Mn(μ-SSitBu 3)2Mn(THF)SSitBu3] (monoclinic, C2/c). Cocrystals of the Mn(I)Mn(II)_species Na(THF)6[(OC) 3Mn(μ-SSitBu3)3MnSSitBu3] with the trisulfane tBu3Si-SSS-SitBu3 (trigonal, R3) are obtained by the reaction of [Mn(CO)5Br] with 2 equiv of Na(THF) 2SSitBu3. The complex anion [(OC)3Mn(μ- SSitBu3)3MnSSitBu3r contains a terminal thiolate ligand with a linear Mn-S-Si unit.
Gusev, O. V.,Krivykh, V. V.,Rybinskaya, M. I.
, (1987)
Redox Reactions of Metal Carbonyls of Group 5A
Calderazzo, Fausto,Pampaloni, Guido
, p. 1249 - 1250 (1984)
Redox reactions of V(CO)6 with -, -, 2-, or 5-C5H5)(CO)3>- (M = Cr, Mo, W), or Co(η5-C5H5)2 occur rapidly at 25 degC and lower in hydrocarbons; on the other hand, V(CO)6 is oxidized to V(η5-C5H5)(CO)4 by Mn(η5-C5H5)2 or Ni(η5-C5H5)2 and the two-electron oxidation of - to the - anion (X = Cl, Br, I, acetylacetonato), can be carried out using a number of oxidizing agents (HgII, CuII, CuI, AgI, or FeIII).
Kolthammer, Brian W. S.,Legzdins, Peter
, (1978)
Heterobimetallic complexes of rhodium dibenzotetramethylaza[14]annulene [(tmtaa)RH-M]: Formation, structures, and bond dissociation energetics
Imler, Gregory H.,Peters, Garvin M.,Zdilla, Michael J.,Wayland, Bradford B.
supporting information, p. 273 - 279 (2015/03/13)
A rhodium(II) dibenzotetramethylaza[14]annulene dimer ([(tmtaa)Rh]2) undergoes metathesis reactions with [CpCr(CO)3]2, [CpMo(CO)3]2, [CpFe(CO)2]2, [Co(CO)4]2, and [Mn(CO)5]2 to form (tmtaa)Rh-M complexes (M = CrCp(CO)3, MoCp(CO)3, FeCp(CO)2, Co(CO)4, or Mn(CO)5). Molecular structures were determined for (tmtaa)Rh-FeCp(CO)2, (tmtaa)Rh-Co(μ-CO)(CO)3, and (tmtaa)Rh-Mn(CO)5 by X-ray diffraction. Equilibrium constants measured for the metathesis reactions permit the estimation of several (tmtaa)Rh-M bond dissociation enthalpies (Rh-Cr = 19 kcal mol-1, Rh-Mo = 25 kcal mol-1, and Rh-Fe = 27 kcal mol-1). Reactivities of the bimetallic complexes with synthesis gas to form (tmtaa)Rh-C(O)H and M-H are surveyed.
Transformation of a phosphorus-bound Cp* moiety in the coordination sphere of manganese carbonyl complexes
Pushkarevsky, Nikolay A.,Konchenko, Sergey N.,Virovets, Alexander V.,Scheer, Manfred
, p. 770 - 779 (2013/03/14)
The reaction of Cp PCl2 with K[Mn(CO)5] yields two novel anionic products, [Mn2(CO)8(μ-PC 11H14O)]- (1-) and [Mn 2(CO)8(μ-PHCp)]- (2-), instead of the expected phosphinidene complexes with a delocalized Mn-P-Mn bond system. By treating these anionic complexes with [Ph3PAuCl], they are converted into corresponding neutral derivatives [Mn2(CO)8(μ- PC11H14O)(μ-AuPPh3)] (3) and [Mn 2(CO)8(μ-PHCp)(μ-AuPPh3)] (4). NMR investigations and X-ray structural analyses for 1-, 3, and 4 show that the compounds 1- and 3 as well as 2- and 4 reveal similar molecular structures in which the neutral complexes 3 and 4 contain AuPPh3 units bridging Mn-Mn bonds. In comparison to 1 and 3, complexes 2 and 4 possess one additional H atom bound at the P atom. The structures of 1 and 3 include a novel bicyclic unit consisting of a C 5 ring of the former Cp* moiety conjugated to a CCC(O)P four-membered ring. The latter is built by a CO group of a former Mn carbonyl fragment connecting a P and a C atom of the cycle. One of the methyl groups of the Cp* ligand became a CH2 unit, resulting in two isomers containing an exocyclic CH2 moiety in the positions three or five of the C5 ring. Both isomers were found in the reaction mixture, with one as the major isomer. The proposed reaction pathway is based on XRD, NMR, and MS data and includes the reduction of a transient [CpP(Mn(CO)5) 2] complex by [Mn(CO)5]-, a proton transfer from the neutral to the reduced complex, and a successive reduction of the protonated species. The neutral bicyclic compound 3, containing a 2-phosphacyclobutanone ring, is light sensitive and decomposes to tetramethylfulvene, possibly by a radical decarbonylation mechanism via a transient phosphacyclobutane derivative, [C5(CH3) 4(CH2)P(Mn(CO)4)2AuPPh3] (5), detected by NMR spectroscopy.
