Reduction of coordinated carbon monoxide. Synthesis of neutral metal formyl and hydroxymethyl derivatives of the (cyclopentadienyl)dicarbonyl(nitrosyl)rhenium(1+) cation

Casey, Charles P.; Andrews, Mark A.; McAlister, Donald R.; RINZ, J. E.

doi:10.1021/ja00526a028

Cited by 109 publications

(34 citation statements)

References 16 publications

(26 reference statements)

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“…The hydride reduction of a ReϪCO group has already been described by Gladysz, [4,17] Casey, [21] Graham [22] and our group. [7] The new methyl complexes 4aϪe were obtained in the same way in good yields as orange or orangered solids [Equation (2)].…”

Section: Methyl Complexessupporting

confidence: 57%

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands

Dilsky

Schenk

2004

Eur J Inorg Chem

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The syntheses and some typical reactions of diastereomeric rhenium complexes [CpRe(NO)(CO){P(Ph)(R)(R′)}]BF4 (R = Me, Ph; R′ = 2‐C6H4OMe, CH2C4H3S, CH2C4H7O) (3a−e) are described. Reduction of the carbonyl ligand with NaBH4 in THF gave the corresponding methyl complexes [CpRe(NO){P(Ph)(R)(R′)}(CH3)] (4a−e). Acid treatment of the methyl complexes leads to liberation of methane and coordination of the additional donor site of the potentially bidentate phosphane ligand. Of the chelate complexes 5a−e, those with R′ = 2‐C6H4OMe (5a, d) decomposed in solution at room temperature. In donor solvents, the chelate ring opens giving the stable solvated complexes [CpRe(NO){P(Ph)(R)(R′)}](solvent)]BF4 (solvent = CH3CN, THF) (6b−e, 7d). The new compounds are thus suitable starting materials for the syntheses of diastereomeric rhenium complexes [CpRe(NO){P(Ph)(R)(R′)}(L)]BF4. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Methyl Complexessupporting

confidence: 57%

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands

Dilsky

Schenk

2004

Eur J Inorg Chem

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“…The observed instability of CpFe(C0)2CH20H (4) augments a growing body of evidence concerning thermal instability of α-hydroxyalkyl complexes (38,39,40,41,42).…”

supporting

confidence: 62%

“…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.…”

mentioning

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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“…Bei der metallkatalysierten Reduktion von Kohlenmonoxid durch Wasserstoff sind in einem primä-ren Reaktionsschritt Formylkomplexe zu erwarten [1][2][3][4][5], deren Hydrierung zu Hydroxymethylkomplexen führt [6][7][8]. Präparativ sind sie vorzugsweise durch Hydridübertragung auf eine M-CO-Funktion zugänglich [4,9].…”

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Rhodium(I)-Komplexe mit 2,5-Difurfurylpyrrol-Liganden / Rhodium(I) Complexes with 2,5-Difurfurylpyrrole Ligands

Lindner¹,

Schneider²,

Fawzi³

et al. 1988

Zeitschrift Für Naturforschung B

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Abstract The 2.5-difurfurylpyrrole-O.N.O ligands 3a, b [R = CO2C2H5 (a). COCH, (b)] are obtained by reaction of the furanes l a , b with the 2,5-bis(chloromethyl)pyrrole 2 in the presence of SnCl4. Proton abstraction from 3a, b with NaH affords the sodium salts 4a-Na and 4b-Na. Exchange of the chlorine bridges in [μ-ClRh(Diol)]2 (5,5') (Diol = cyclooctadiene, norbornadiene) results in the formation of the 14-electron complexes (Diol)Rh(O.N.O) (6a,6'a). Addition of PPh3, yields the four-coordinated rhodium complexes (Diol)Rh(O.N.O)(PPh3) (7a,7'a). These compounds are also available in a reverse reaction sequence from 5,5', PPh3, and 4a-Na. The mononuclear rhodium complexes RhCl(Diol)(PPh3) (8,8') are isolated as intermediates. In 7a, 7'a the olefinic ligands are replaced by carbon monoxide to give the dicarbonyl rhodium complex (OC)2Rh(O.N.O)(PPh3) (9a) being detectable only in solution. The same result is achieved upon addition of CO to the compound (OC)Rh(O.N.O)(PPh,) (11a) which results bv the reaction of [μ-ClRh(CO)(PPh3)]2 (10) with 4a-Na. Oxidative addition of CH3I or H2 to 6a, 6 a, 7a, 7'a or 11a was not observed. 1H and 31P{1H} NMR investigations indicate that depending on the temperature the O.N.O ligand in the 14-electron rhodium complex 11a acts as tri- (11a-A), bi- (11a-B) and monodentate (IIa-C) ligands. respectively. 11a also reacts with PPh, to form the /ram-bis(phosphane)rhodium complex (PPh3)2Rh(CO)(O.N.O) (12a). 12a and the analogous complexes 12b and trans-(PMe3)2Rh(CO)(O,N.O) (14a) are obtained by action of ClRh(CO)L2 (13) (L = PPh3. PMe3) on 4a-Na and 4b-Na, respectively. The methylene bridges in the O.N.O ligand 3a are not oxidized, neither in the non-complexed (3a) nor in the complexed (12a) state. According to an X-ray structural analysis 14a crystallizes in the monoclinic space group P21/n with Z = 4. In 6a, 6'a, 7a, 7'a, 9a, 11a, 12a, b, and 14a the O.N.O ligand is always nitrogen bonded

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Reduction of coordinated carbon monoxide. Synthesis of neutral metal formyl and hydroxymethyl derivatives of the (cyclopentadienyl)dicarbonyl(nitrosyl)rhenium(1+) cation

Cited by 109 publications

References 16 publications

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands

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

Rhodium(I)-Komplexe mit 2,5-Difurfurylpyrrol-Liganden / Rhodium(I) Complexes with 2,5-Difurfurylpyrrole Ligands

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Reduction of coordinated carbon monoxide. Synthesis of neutral metal formyl and hydroxymethyl derivatives of the (cyclopentadienyl)dicarbonyl(nitrosyl)rhenium(1+) cation

Cited by 109 publications

References 16 publications

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands

Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile Phosphane Ligands

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

Rhodium(I)-Komplexe mit 2,5-Difurfurylpyrrol-Liganden / Rhodium(I) Complexes with 2,5-Difurfurylpyrrole Ligands

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