Aspects of homogeneous carbon monoxide fixation: selective conversion of two carbonyl ligands on (.eta.5-C5H5)Fe(CO)3+ to C2 organic compounds

Bodnar, T. W.; Coman, Gene; LACROCE, S. J.; Lambert, Carol; Menard, Kevin P.; Cutler, Alan R.

doi:10.1021/ja00399a083

Cited by 27 publications

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“…Like the above hydride migration, deprotonation is stereoselective, leading to the vinyl isomer in which the alkoxy groups are trans to one another. Deprotonation of cationic rhenium carbenes has previously been found to lead to rhenium vinyl complexes. − In contrast, Cutler found that the analogous iron carbene will accept a hydride from LiHBEt 3 . , Placing a methanol solution of 16 under 1000 psi of CO does not lead to observable carbonylation products.…”

Section: Resultsmentioning

confidence: 99%

Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme

et al. 2009

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A variety of C-H and C-C bond forming reactions of group 7 carbonyl complexes have been studied as potential steps in a homogeneously catalyzed conversion of syngas to C 2þ compounds. The metal formyl complexes M(CO) 3 (PPh 3 ) 2 (CHO) (M=Mn, Re) are substantially stabilized by coordination of boranes BX 3 (X = F, C 6 F 5 ) in the form of novel boroxycarbene complexes M(CO) 3 -(PPh 3 ) 2 (CHOBX 3 ), but these boron-stabilized carbenes do not react with hydride sources to undergo further reduction to metal alkyls. The related manganese methoxycarbene cations [Mn(CO) 5-x (PPh 3 ) x (CHOMe)] þ (x=1 or 2), obtained by methylation of the formyls, do react with hydrides to form methoxymethyl complexes, which undergo further migratory insertion under an atmosphere of CO. The resulting acyls, cis-and trans-Mn(PPh 3 )(CO) 4 (C(O)CH 2 OMe), can be alkylated to form the cationic carbene complex [Mn(PPh 3 )(CO) 4 (C(OR)CH 2 OMe)] þ , which undergoes a 1,2 hydride shift to form 1,2-dialkoxyethylene, which is displaced from the metal, releasing triflate or diethyl ether adducts of [Mn(PPh 3 )(CO) 4 ] þ . The acyl can also be protonated with HOTf to form a hydroxycarbene complex, which rearranges to Mn(PPh 3 )(CO) 4 (CH 2 COOMe) and is protonolyzed to yield methyl acetate and [Mn(PPh 3 )(CO) 4 ] þ ; addition of L (L = PPh 3 , CO) to the manganese cation regenerates [Mn(PPh 3 )(CO) 4 (L)] þ . Since the original formyl complex can be obtained by the reaction of [Mn(PPh 3 )(CO) 5 ] þ with [PtH(dmpe) 2 ] þ , which in turn can be generated from H 2 , this set of transformations amounts to a stoichiometric cycle for selectively converting H 2 and CO into a C 2 compound under mild conditions.

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Section: Resultsmentioning

confidence: 99%

Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme

et al. 2009

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“…After a number of attempts using various bases and solvents, ethanolic KOH was found to deprotonate 2 conveniently forming a dianion, which could be obtained as an analytically pure yellow solid with large counterions such as Et4N+ or (Ph3P)2N+ (eq 5). Elemental analysis (11) Moss, J. R.; Graham, W. A. G. J. Organomet. Chem.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and reactions of dicarbonyl(.eta.-cyclopentadienyl)dihydridorhenium(III)

Hoyano¹,

Graham²

1982

Organometallics

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the basis of steric requirements due to the larger coordination number and of the different oxidation number of the metal. ConclusionsThe triethylphosphine-carbon disulfide adduct Et3P-CS2 is a very versatile ligand. Indeed this zwitterion can act as a monodentate or bidentate donor by means of its electron-rich sulfur atoms, but it can be also bonded to Synthesis and Reactions of Dicarbonyl(77-cyclopentadienyl)dihydridorhenium(III)

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With Trialkylborohydride and Other Substituted Borohydrides

Norton¹

1987

Inorganic Reactions and Methods

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Aspects of homogeneous carbon monoxide fixation: selective conversion of two carbonyl ligands on (.eta.5-C5H5)Fe(CO)3+ to C2 organic compounds

Cited by 27 publications

References 0 publications

Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme

Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme

Synthesis and reactions of dicarbonyl(.eta.-cyclopentadienyl)dihydridorhenium(III)

With Trialkylborohydride and Other Substituted Borohydrides

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