Transition metal formyl complexes: Synthesis by trialkylborohydride attack on metal carbonyl acyls

Gladysz, J. A.; Selover, J. C.

doi:10.1016/s0040-4039(01)85114-5

Cited by 33 publications

(8 citation statements)

References 10 publications

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“…The ab-initio calculations were carried out with the system of programs Asterix [11] using the following basis sets: (13,8,6) contracted to [5,3,3] for iron [12], (9,5) contracted to [3,2] for the first-row atoms [13] and (6) contracted to [3] for hydrogen [14]: the contracted basis set is a minimal set for the inner shells, a double-zeta for the valence'shells and a triple-zeta for the 3d of iron and for the hydrogen atom. Our choice of a triple-zeta contracted basis set for the hydrogen atom was determined by the requisite of a fairly balanced description of the interacting hydride at long and short C--H distances [15].…”

Section: The Calculationsmentioning

confidence: 99%

“…The reactions of suitable hydride sources with metal carbonyl complexes to yield formyl complexes have been recently evidenced [1][2][3][4][5]. Such formyl complexes are believed to occur as reactive intermediates in many catalytic or stoechiometric processes [1].…”

Section: Introductionmentioning

confidence: 99%

“…They can also be regarded as a first step in the activation of carbon monoxide towards reduction [1,6]. We present here the results of LCAO-MO-SCF ab-initio calculations for the nucleophilic addition of the hydride anion Hon the iron pentacarbonyl complex Fe(CO)5 1 to give the formyl complex (CO)4Fe(CHO)-2 (where experimentally [2][3][4]7] the hydride is released by appropriate hydride donors). We present here the results of LCAO-MO-SCF ab-initio calculations for the nucleophilic addition of the hydride anion Hon the iron pentacarbonyl complex Fe(CO)5 1 to give the formyl complex (CO)4Fe(CHO)-2 (where experimentally [2][3][4]7] the hydride is released by appropriate hydride donors).…”

Section: Introductionmentioning

confidence: 99%

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Ab-initio SCF potential energy surfaces for the nucleophilic attack of hydride on coordinated carbon monoxide

Nakamura

Dedieu

1982

Theoret. Chim. Acta

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Ab-initio SCF calculations are reported for the nucleophilic addition of the hydride ion H-on the iron pentacarbonyl Fe(CO)5 complex. The stereochemistry of the attack has been established from the determination of two potential energy surfaces. The reaction is shown to be highly exothermic and with no activation barrier. This activation of CO towards the nucleophilic addition is rationalized in terms of molecular orbital interactions.

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Section: The Calculationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ab-initio SCF potential energy surfaces for the nucleophilic attack of hydride on coordinated carbon monoxide

Nakamura

Dedieu

1982

Theoret. Chim. Acta

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“…Until properly activated, transition metal acyl complexes generally do not add nucleophiles (59), including hydride from nucleophilic hydride-donating reagents (60, 61,62), to the acyl functionality.…”

Section: Selective Conversion Of Carbonyls To C2smentioning

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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“…A variety of formyl complexes have been synthesized [45][46][47][48][49][50][51][52][53][54], and at least some of them can be reduced to yield fo:r:rnaldehyde or methanol l54,55J. Intrared spectroscopic evidence for the formation of formyl by coadsorbed CO and H 2 on Cu/ZnO at nearambient conditions has been reported [56].…”

Section: Chemical Trapping Of Surface Intermediates On Thementioning

confidence: 99%

Methanol and methyl fuel catalysts. Final technical report, September 1978-August 1980

Klier¹,

Herman²

1980

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Transition metal formyl complexes: Synthesis by trialkylborohydride attack on metal carbonyl acyls

Cited by 33 publications

References 10 publications

Ab-initio SCF potential energy surfaces for the nucleophilic attack of hydride on coordinated carbon monoxide

Ab-initio SCF potential energy surfaces for the nucleophilic attack of hydride on coordinated carbon monoxide

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

Methanol and methyl fuel catalysts. Final technical report, September 1978-August 1980

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Transition metal formyl complexes: Synthesis by trialkylborohydride attack on metal carbonyl acyls

Cited by 33 publications

References 10 publications

Ab-initio SCF potential energy surfaces for the nucleophilic attack of hydride on coordinated carbon monoxide

Ab-initio SCF potential energy surfaces for the nucleophilic attack of hydride on coordinated carbon monoxide

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

Methanol and methyl fuel catalysts. Final technical report, September 1978-August 1980

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