Neutral metal formyl complexes: generation, reactivity, and models for Fischer-Tropsch catalyst intermediates

Tam, William; Wong, Wai‐Kwok; Gladysz, J. A.

doi:10.1021/ja00500a037

Cited by 109 publications

(44 citation statements)

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“…This also includes nitrosyl compounds, which represent a large family of complexes in the chemistry of the heavier congener rhenium. Complexes of the compositions [Re(NO)(L)(Cp)(PPh 3 )] 0,+ , where L represents a large variety of ligands, are known for many years and a fascinating chemistry has been established comprising more than 100 papers and 200 crystal structures [23–34] . However, a key complex of this class of compounds, [Re(NO)Cl(Cp)(PPh 3 )] ( 1 b ), is synthesized in a multiple‐step synthesis starting from Re 2 (CO) 10 (Scheme 1), which is less favored for the radioactive element technetium.…”

Section: Introductionmentioning

confidence: 99%

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

2021

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Reactions of the chiral organometallic technetium(I) compound [Tc(NO)Cl(Cp)(PPh3)] (1 a) with phosphines and alkynes give unexpected products such as the dimeric cation [{Tc(NO)(Cp)(PPh3)}2Cl]+ (4) or the Fischer‐type carbene [Tc(NO)(Cp)(PPh3){C(OR)C2H4PPh3}]2+ (5). Both products could be isolated as PF6− salts and studied by spectroscopic methods and X‐ray diffraction. While [Tc(NO)(Cp)(PMe3)(PPh3)](PF6) (2PF6) can be obtained from 1 a, PMe3 and Ag(PF6) under ambient conditions, the synthesis of the corresponding bis‐triphenylphosphine complex [Tc(NO)(Cp)(PPh3)2](PF6) (3PF6) requires high temperatures and long reaction times. The products are stable in air.

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Section: Introductionmentioning

confidence: 99%

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

2021

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“…A variety of formyl complexes have been synthesized [45][46][47][48][49][50][51][52][53][54] In general, amines are known to react with aldehydes and ketones to produce alkyl substituted amines and water [57]: (11) where R=H or alkyl. The reaction is a typical nucleophilic addition of the electron-rich (base) nitrogen of the amine attacking the electron-deficient (acid) carbonyl carbon of the aldehyde or ketone.…”

Section: 30mentioning

confidence: 99%

Methanol and methyl fuel catalysts. Final technical report, September 1980-August 1983

Klier¹,

Herman²,

Simmons³

1983

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Price: Printed Copy A06 Microfiche AOl Codes are used for pricing all publications. The code is determined by the number of pages in the publication. Information pertaining to the pricing codes can be found in the current issues of the following publications, which are generally available in most libraries: Energy Research Abstracts (ERA); Government Reports Announcements and Index (GRA and I); Scientific and Technical

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“…Complexes bearing P2~acyl ligands are rare (75) , but they are recognized now as a means of stabilizing and activating formyl ligands to reduction (35,76,77). Lewis acid activation of other acyl ligands has been established with n 2 -acyl complexation to a metal (78,79), and with BH 3 reduction of r^-acetyl (60) and r^-formyl (38,48) complexes. Other Lewis acids such as Al(III) (52) or Li(I) (80) also facilitate alkyl-acyl migratory-insertion reactions through complexation of the incipient acyl ligand (75).…”

Section: Towards Catalytic Relevance: Bimetallic Activation Of Acyl Lmentioning

confidence: 99%

“…Indeed, the facile reduction of a CO ligand on CpRe(C0) 2 N0 + (38,39,48) or on CpMo(CO) 3 PPh 3 + (48,49) with borohydride reagents (giving for example isolable rv^-formyl, hydroxymethyl, and methyl complexes of CpRe(CO)NO) appear anomolous. Perhaps this paucity of examples for stoichiometric CO fixation reflects in part the limited number of reducing media investigated.…”

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confidence: 99%

Aspects of Homogeneous Carbon Monoxide FixationSelective Conversion of Carbonyl Ligands on (η₅-C₅H₅)Fe(CO)₃⁺ to C₂ Organic Compounds

Cutler

Bodnar

Coman

et al. 1981

ACS Symposium Series

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Procurement of transition metal catalysts that convert carbon monoxide and dihydrogen to organic molecules represents an important research objective of modern inorganic chemistry. Im petus for this research derives from the use of coal, a source of CO/H 2 synthesis gas mixtures, as a future source of petrochemi cals (1). Although heterogeneous catalysis in the FischerTropsch synthesis (2,3) of complex hydrocarbon mixtures from synthesis gas has long been established, homogeneous catalysis of these reactions would have the added advantage of a potentially high and manipulative product selectivity.A selective homoge neous catalytic synthesis of C 2 organics -especially C 2 -oxygenates such as ethylene glycol (4), acetaldehyde, and acetic acidwould provide a much desired coal-based source of organic feed stocks (1).One approach favored by us for the rational design of such catalysts first requires an understanding of reaction pathways by which ligated CO undergoes hydrogenation and subsequent syn thesis reactions (ie. chain growth of the C 1 ligand), before eliminating the desired organic molecule. Fully characterized organometallic complexes are used as model systems to collect this mechanistic information.Then more labile (and hopefully catalytic) systems are designed and tested. Limited mechanistic data is now available for stoichiometric conversion of CO ligands to the C2 organic compounds ethane Ç5,6^7), ethylene (6,8), acetaldehyde (9), methylacetate (10), and a coordinated enediol of glycolaldehyde (11). Clearly a need exists for more extensive information on CO fixation and synthesis reaction pathways.We have delineated viable coordinated ligand reactions and their attendant intermediates for the stoichiometric conversion of CO ligands selectively to the C2 organics ethane, ethylene, methyl (or ethyl) acetate, and acetaldehyde.We now outline results from three lines of research:(1) r^-Alkoxymethyl iron complexes CpFe(C0)2CH20R (2) are available by reducing coordinated CO on CpFe(C0)3+ (1) [Cp = n 5 -C5H5]. Compounds 2 then form r^-alkoxyacetyl complexes via migratory-insertion (i .e. CO

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Neutral metal formyl complexes: generation, reactivity, and models for Fischer-Tropsch catalyst intermediates

Cited by 109 publications

References 3 publications

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

Methanol and methyl fuel catalysts. Final technical report, September 1980-August 1983

Aspects of Homogeneous Carbon Monoxide FixationSelective Conversion of Carbonyl Ligands on (η₅-C₅H₅)Fe(CO)₃⁺ to C₂ Organic Compounds

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Neutral metal formyl complexes: generation, reactivity, and models for Fischer-Tropsch catalyst intermediates

Cited by 109 publications

References 3 publications

[Tc(NO)Cl(Cp)(PPh3)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

[Tc(NO)Cl(Cp)(PPh3)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

Methanol and methyl fuel catalysts. Final technical report, September 1980-August 1983

Aspects of Homogeneous Carbon Monoxide FixationSelective Conversion of Carbonyl Ligands on (η5-C5H5)Fe(CO)3+ to C2 Organic Compounds

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[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

[Tc(NO)Cl(Cp)(PPh₃)] – A Technetium(I) Compound with an Unexpected Synthetic Potential

Aspects of Homogeneous Carbon Monoxide FixationSelective Conversion of Carbonyl Ligands on (η₅-C₅H₅)Fe(CO)₃⁺ to C₂ Organic Compounds