Reductive Coupling Of Carbon Monoxide Research Articles

Hydrodeoxygenative Cyclotetramerization of Carbon Monoxide by a Trinuclear Titanium Polyhydride Complex.

The reductive coupling of carbon monoxide (CO) by metal hydrides is of fundamental interest and practical importance. Herein we report an unprecedented hydrodeoxygenative cyclotetramerization of CO by a trinuclear titanium polyhydride complex [(C5Me4SiMe3)Ti]3(μ3-H)(μ2-H)6 (1). The reaction of CO with 1 at -78 °C gave an ethen-1,2-diyl species [CH═CH]2- through the hydrodeoxygenative dimerization of two molecules of CO, which upon cycloaddition to another two molecules of CO afforded a cyclobuten-3,4-diyl-1,2-diolate unit [C4H2O2]4-. The hydrogenolysis of the [C4H2O2]4- species with H2 yielded a tetrahydrocyclobuten-1,2-diolate species [C4H4O2]2-, which on heating at 100 °C gave a cyclobuten-2-yl-1-olate product [C4H4O]2-. The acidolysis of the [C4H2O2]4- and [C4H4O]2- species with HCl afforded γ-butyrolactone and cyclobutanone, respectively.

Ru3(CO)12-Catalyzed Reaction of 1,6-Diynes, Carbon Monoxide, and Water via the Reductive Coupling of Carbon Monoxide.

We report the ruthenium-catalyzed cyclization of 1,6-diynes with two molecules of carbon monoxide and water to give a variety of catechols. This reaction likely proceeds through the intermediacy of the water-gas shift reaction to generate an yne-diol-type intermediate followed by a [4 + 2] cycloaddition with 1,6-diynes. The reaction requires no external reductants or hydride sources and provides a novel and valuable method for the synthesis of a variety of catechols.

Reductive coupling of carbon monoxide to glycolaldehyde and hydroxypyruvaldehyde polyanions in binuclear cyclopentadienyl lanthanum and lutetium derivatives: analogies to cyclooctatetraene thorium chemistry

Cloke and coworkers have recently (2006–2012) shown that reaction of carbon monoxide with organouranium compounds results in reductive coupling to yield the oligomeric anions C n O 2− (n = 2, 3, 4). In order to explore the possibilities of similar reductive coupling of carbon monoxide in organolanthanide systems, the structures and thermochemistry of the cyclopentadienyllanthanide carbonyls Cp2Ln2(CO) n (n = 2, 3, 4, 5) have been investigated using lanthanum and lutetium, which are diamagnetic in the favored +3 oxidation state. All of these Cp2Ln2(CO) n structures have long Ln···Ln distances exceeding 4.2 A for La and 3.6 A for Lu, indicating the lack of direct metal–metal bonding and suggesting the normally favored +3 oxidation state for these lanthanides. In the dicarbonyls Cp2Ln2(CO)2, the two CO groups couple to form a bridging µ-C2O2 4− ligand, which can be derived by removal of four protons from glycolaldehyde (hydroxyacetaldehyde). Similarly, in the tricarbonyls, the three CO groups couple to form a bridging µ-C3O3 4− ligand, which can be derived by removal of four protons from hydroxypyruvaldehyde. However, the lowest energy structures for the tetracarbonyls Cp2Ln2(CO)4 (by more than 13 kcal/mol) have four separate η2-µ-CO ligands bonded to the central Ln2 unit through both their carbon and oxygen atoms. Thermochemistry of the Cp2Ln2(CO) n systems suggests viability of Cp2Ln2(CO)2 and Cp2Ln2(CO)4. However, Cp2Ln2(CO)3 is predicted to be disfavored relative to disproportionation into Cp2Ln2(CO)2 + Cp2Ln2(CO)4.

Four-electron deoxygenative reductive coupling of carbon monoxide at a single metal site.

Carbon dioxide is the ultimate source of the fossil fuels that are both central to modern life and problematic: their use increases atmospheric levels of greenhouse gases, and their availability is geopolitically constrained. Using carbon dioxide as a feedstock to produce synthetic fuels might, in principle, alleviate these concerns. Although many homogeneous and heterogeneous catalysts convert carbon dioxide to carbon monoxide, further deoxygenative coupling of carbon monoxide to generate useful multicarbon products is challenging. Molybdenum and vanadium nitrogenases are capable of converting carbon monoxide into hydrocarbons under mild conditions, using discrete electron and proton sources. Electrocatalytic reduction of carbon monoxide on copper catalysts also uses a combination of electrons and protons, while the industrial Fischer-Tropsch process uses dihydrogen as a combined source of electrons and electrophiles for carbon monoxide coupling at high temperatures and pressures. However, these enzymatic and heterogeneous systems are difficult to probe mechanistically. Molecular catalysts have been studied extensively to investigate the elementary steps by which carbon monoxide is deoxygenated and coupled, but a single metal site that can efficiently induce the required scission of carbon-oxygen bonds and generate carbon-carbon bonds has not yet been documented. Here we describe a molybdenum compound, supported by a terphenyl-diphosphine ligand, that activates and cleaves the strong carbon-oxygen bond of carbon monoxide, enacts carbon-carbon coupling, and spontaneously dissociates the resulting fragment. This complex four-electron transformation is enabled by the terphenyl-diphosphine ligand, which acts as an electron reservoir and exhibits the coordinative flexibility needed to stabilize the different intermediates involved in the overall reaction sequence. We anticipate that these design elements might help in the development of efficient catalysts for converting carbon monoxide to chemical fuels, and should prove useful in the broader context of performing complex multi-electron transformations at a single metal site.

Reductive coupling of carbon monoxide by U(iii) complexes—a computational study

The role of U((η-C(8)H(6){Si(i)Pr(3)-1,4}(2))(η-C(5)Me(5)) and U((η-C(8)H(6){Si(i)Pr(3)-1,4}(2))(η-C(5)Me(4)H) in the reductive di- tri- and tetramerization of CO has been modelled using density functional methods and U(C(8)H(8))(C(5)H(5)) as the metal fragment. The orbital structure of U(C(8)H(8))(C(5)H(5)) is described. CO binding to form a monocarbonyl U(C(8)H(8))(C(5)H(5))(CO) is found, by a variety of methods, to place spin density on the CO ligand via back-bonding from the U5f orbitals. A possible pathway for formation of the yne diolate complex [U(C(8)H(8))(C(5)H(5))](2)C(2)O(2) is proposed which involves dimerization of U(C(8)H(8))(C(5)H(5))CO via coordination of the CO O atoms to the opposing U atoms followed by C-C bond formation to form a zig-zag intermediate, stable at low temperatures. The intermediate then unfolds to form the yne diolate. The structures of [U(C(8)H(8))(C(5)H(5))]C(2)O(2), the deltate complex [U(C(8)H(8))(C(5)H(5))]C(3)O(3) and the squarate complex [U(C(8)H(8))(C(5)H(5))]C(4)O(4) are optimized and provide good models for the experimental compounds. The reaction of further CO with a zig-zag intermediate to form deltate and squarate complexes was explored using Th(C(8)H(8))(C(5)H(5)) as a model and low energy pathways are proposed.

Homogeneous CO Hydrogenation: Ligand Effects on the Lewis Acid-Assisted Reductive Coupling of Carbon Monoxide

Structure−function studies on the role of pendent Lewis acids in the reductive coupling of CO are reported. Cationic rhenium carbonyl complexes containing zero, one, or two phosphinoborane ligands (Ph2P(CH2)nB(C8H14), n = 1−3) react with the nucleophilic hydride [HPt(dmpe)2]+ to reduce [M−CO]+ to M−CHO; this step is relatively insensitive to the Lewis acid, as both pendent (internal) and external boranes of appropriate acid strength can be used. In contrast, whether a second hydride transfer and C−C bond forming steps occur depends strongly on the number of carbon atoms between P and B in the phosphinoborane ligands, as well as the number of pendent acids in the complex: shorter linker chain lengths favor such reductive coupling, whereas longer chains and external boranes are ineffective. A number of different species containing partially reduced CO groups, whose exact structures vary considerably with the nature and number of phosphinoborane ligands, have been crystallographically characterized. The reac...

ChemInform Abstract: Reductive Coupling of Carbon Monoxide and Alkyl Isocyanide Ligands in Early Transition Metal Complexes: A Review

ChemInform Abstract: Reductive Coupling of Carbon Monoxide and Alkyl Isocyanide Ligands in Early Transition Metal Complexes: A Review

Reductive Coupling of Carbon Monoxide in a Rhenium Carbonyl Complex with Pendant Lewis Acids

Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C-C bond has been formed between two reduced CO ligands. This product of C-C bond formation can be independently synthesized by addition of 2 equiv of hydride to the rhenium carbonyl cation.

Reductive Coupling of Carbon Monoxide with Alkynes Leading to a Novel Case of Carbon-Oxygen Bond Formation. The First Examples of 3-Metallafuran Complexes

Reductive Coupling of Carbon Monoxide with Alkynes Leading to a Novel Case of Carbon-Oxygen Bond Formation. The First Examples of 3-Metallafuran Complexes

Use of dirhenium complexes as templates for the reductive coupling of carbon monoxide with alkynes through carbon-oxygen bond formation. Synthesis and characterization of 3-metallafuran complexes

Use of dirhenium complexes as templates for the reductive coupling of carbon monoxide with alkynes through carbon-oxygen bond formation. Synthesis and characterization of 3-metallafuran complexes

Formation of highly functionalized metal-bound acetylenes by reductive coupling of carbon monoxide and methyl isocyanide ligands

Reduction of [M(CNMe)(CO)(dmpe) 2 Cl] (M=Nb, Ta; dmpe=1,2-bis(dimethylphosphino)ethane) with 40% Na/Hg followed by addition of Me 3 SiCl achieved the reductive coupling of the CO and CNMe ligands to form [M{(Me 3 Si)(Me)NC≡CO(SiMe 3 )}(dmpe) 2 Cl]. The niobium complex was characterized in a single-crystal X-ray diffraction study, which revealed the presence of the unprecedented RR'NC≡COR acetylene ligand

Vanadium-promoted reductive coupling of carbon monoxide and facile hydrogenation to form cis-disiloxyethylenes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTVanadium-promoted reductive coupling of carbon monoxide and facile hydrogenation to form cis-disiloxyethylenesJohn D. Protasiewicz and Stephen J. LippardCite this: J. Am. Chem. Soc. 1991, 113, 17, 6564–6570Publication Date (Print):August 1, 1991Publication History Published online1 May 2002Published inissue 1 August 1991https://doi.org/10.1021/ja00017a030RIGHTS & PERMISSIONSArticle Views526Altmetric-Citations72LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (922 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Mechanistic studies of the reductive coupling of carbon monoxide in seven-coordinate niobium(I) and tantalum(I) dicarbonyl complexes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMechanistic studies of the reductive coupling of carbon monoxide in seven-coordinate niobium(I) and tantalum(I) dicarbonyl complexesRaymond N. Vrtis, Shuncheng Liu, C. Pulla Rao, Simon G. Bott, and Stephen J. LippardCite this: Organometallics 1991, 10, 1, 275–285Publication Date (Print):January 1, 1991Publication History Published online1 May 2002Published inissue 1 January 1991https://doi.org/10.1021/om00047a061RIGHTS & PERMISSIONSArticle Views191Altmetric-Citations45LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

ChemInform Abstract: Reductive Coupling of Carbon Monoxide with Methyl Isocyanide in a Seven‐Coordinate Niobium Complex.

AbstractWhen the novel isocyanide‐carbonyl compound (III) is subjected to reductive coupling conditions an unprecedented acetylene ligand is formed by a cross‐coupling of CO and CN‐Me.

Reductive coupling of carbon monoxide with methyl isocyanide in a seven-coordinate niobium complex

Reductive coupling of carbon monoxide with methyl isocyanide in a seven-coordinate niobium complex

Reductive Coupling of Carbon Monoxide and Alkyl Isocyanide Ligands in Early Transition Metal Complexes: A Review

Israel Journal of ChemistryVolume 30, Issue 4 p. 331-341 Article Reductive Coupling of Carbon Monoxide and Alkyl Isocyanide Ligands in Early Transition Metal Complexes: A Review Raymond N. Vrtis, Raymond N. Vrtis Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USASearch for more papers by this authorStephen J. Lippard, Corresponding Author Stephen J. Lippard Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USADepartment of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USASearch for more papers by this author Raymond N. Vrtis, Raymond N. Vrtis Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USASearch for more papers by this authorStephen J. Lippard, Corresponding Author Stephen J. Lippard Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USADepartment of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USASearch for more papers by this author First published: 1990 https://doi.org/10.1002/ijch.199000035Citations: 42AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Citing Literature Volume30, Issue4Special Issue: Organometallic Models and Mechanisms (Part A)1990Pages 331-341 RelatedInformation

Selective reductive coupling of carbon monoxide

Tetra-(3,5 dimethylphenyl)porphyrinato rhodium(II)dimer, [(TXP)Rh]2, reacts reversibly with CO to form a 1,2-ethanedionyl complex, (TXP)Rh–C(O)C(O)–Rh(TXP), which constitutes the first well-characterized example of reductive coupling of CO to form a dimetal α-diketone species.

Complex CO–potassium interactions on Cu(100): An electron energy loss, thermal desorption, and work function study

A detailed examination of the adsorption states of carbon monoxide on a potassium-dosed Cu(100) surface is reported. High resolution electron energy loss spectroscopy (EELS) studies on surfaces with a variety of potassium precoverages indicate the presence of at least seven different C–O vibrational modes ranging in frequency from 900 to 2090 cm−1 with as many as five modes observed simultaneously. Thermal desorption spectroscopy (TDS) demonstrates at least five states of CO coadsorbed with potassium with desorption maxima occuring over a range from 120 to 600 K. Low resolution EELS and work function changes are discussed as well. The complexity of the high resolution EELS and TDS measurements precludes models involving only one or two types of potassium–CO interactions. In this system we suggest that potassium influences CO adsorption by, (1) indirectly increasing 2π* backbonding, (2) indirectly changing bonding sites, and (3) effecting a direct interaction of adsorbed CO with one, two, or possibly three neighboring potassium adatoms. Although we find no conclusive evidence for the reductive coupling of carbon monoxide to form discrete (CO)n–K polyhedral complexes at high potassium surface coverages, we cannot rule out the formation of such species.

Hydriodic acid-induced reductive coupling of carbon monoxide and homologation of a carboxylic acid

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHydriodic acid-induced reductive coupling of carbon monoxide and homologation of a carboxylic acidLeonard KaplanCite this: J. Org. Chem. 1982, 47, 27, 5422–5424Publication Date (Print):December 1, 1982Publication History Published online1 May 2002Published inissue 1 December 1982https://doi.org/10.1021/jo00148a048RIGHTS & PERMISSIONSArticle Views70Altmetric-Citations8LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (468 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Transition metal/acid-induced reductive coupling of carbon monoxide

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition metal/acid-induced reductive coupling of carbon monoxideLeonard KaplanCite this: J. Org. Chem. 1982, 47, 27, 5424–5425Publication Date (Print):December 1, 1982Publication History Published online1 May 2002Published inissue 1 December 1982https://doi.org/10.1021/jo00148a049RIGHTS & PERMISSIONSArticle Views55Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (266 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts