Radical Processes in the Reduction of Nitrobenzene Promoted by Iron Carbonyl Clusters. X-ray Crystal Structures of [Fe3(CO)9(.mu.3-NPh)]2-, [HFe3(CO)9(.mu.3-NPh)]-, and the Radical Anion [Fe3(CO)11]-.bul.

Ragaini, Fabio; Song, Jeong-Sup; Ramage, David L.; Geoffroy, Gregory L.; Yap, Glenn; Rheingold, Arnold L.

doi:10.1021/om00001a054

Cited by 58 publications

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“…In particular, the ν b CO bands become more and more intense as the negative charge increases, according to the general observation that an increase of the negative charge of a cluster leads to an increased tendency for CO ligands to display a bridging coordination mode. 42 All these observations, together with the complete chemical reversibility of the redox processes occurring between +0.3 and −2.4 V, point out that the structure of [Pt 33 (CO) 38 ] n is stable with a variable number of electrons, but some The two most cathodic reduction processes of the cluster are masked, in the voltammetric profile of Figure 8d, by the solvent discharge, but they are well-documented by the spectroelectrochemical experiments (see Figures S.9 and S.10 in Supporting Information). Gas evolution and fast modification of the spectra, at potential beyond −2.7 V, pointed out decomposition of the electrogenerated cluster.…”

Section: Resultsmentioning

confidence: 99%

Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt₃₃(CO)₃₈]^2– and the bcc [Pt₄₀(CO)₄₀]^6– Molecular Nanoclusters

et al. 2016

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The molecular [Pt33(CO)38](2-) nanocluster was obtained from the thermal decomposition of Na2[Pt15(CO)30] in methanol. The reaction of [Pt19(CO)22](4-) with acids (1-2 equiv) affords the unstable [Pt19(CO)22](3-) trianion, which evolves with time leading eventually to the [Pt40(CO)40](6-) hexa-anion. The total structures of both nanoclusters were determined via single-crystal X-ray diffraction. [Pt33(CO)38](2-) displays a defective ccp Pt33 core and shows that localized deformations occur in correspondence of atomic defects to "repair" them. In contrast, [Pt40(CO)40](6-) shows a bcc Pt40 core and represents the largest Pt cluster with a body-centered structure. The rich electrochemistry of the two high-nuclearity platinum carbonyl clusters was studied by cyclic voltammetry and electrochemical in situ Fourier transform infrared spectroscopy. The redox changes of [Pt33(CO)38](2-) show features of chemical reversibility and electrochemical quasi-reversibility, and the vibrational spectra in the CO stretching region of the nine redox forms of the cluster [Pt33(CO)38](n) (n = 0 to -4, -6 to -9) are reported. Almost all the redox processes exhibited by [Pt40(CO)40](6-) are chemically and electrochemically reversible, and the eight oxidation states of [Pt40(CO)40] from -4 to -11 were spectroscopically characterized. The effect of the more regular bcc Pt-carbonyl cluster structure of [Pt40(CO)40](6-) with respect to that of the defective ccp Pt33 core on the redox behavior is discussed.

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Section: Resultsmentioning

confidence: 99%

Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt₃₃(CO)₃₈]^2– and the bcc [Pt₄₀(CO)₄₀]^6– Molecular Nanoclusters

et al. 2016

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“…As far as the activation of nitroarenes by transition metal carbonyl complexes is concerned, the initial step of the reaction has been shown to involve a single electron transfer from the metal to the nitroarene in all the cases in which it has been investigated. These include the use of nickel, [9] ruthenium, [10][11] iron, [12][13][14][15] and rhodium [16][17][18] complexes. No direct evidence for a single electron transfer has been reported in the case of palladium complexes, the metal most widely employed as catalysts, but evidence for radical formation in the activation of nitrosoarenes has been obtained.…”

Section: Mode Of Activation Of the Nitro Groupmentioning

confidence: 99%

“…In the early literature, ruthenium and rhodium carbonyl clusters (Ru 3 (CO) 12 , Rh 4 (CO) 14 , Rh 6 (CO) 16 ) were mostly employed as catalysts for the reductive cyclization of nitroarenes by CO. However, forcing conditions were usually needed to effect the reaction.…”

Section: Catalystsmentioning

confidence: 99%

Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

2019

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Nitroarenes are the entry point for the production of most nitrogen‐containing aromatic compounds. Thus, any transformation that leads directly from them to the final product allows saving one or more synthetic steps. This review deals with homogeneously catalyzed reactions leading to the formation of N‐heterocyclic compounds from nitroarenes or nitroalkenes in one pot. Reactions that lead to the intermediate formation of amines are not considered. Carbon monoxide is the most often employed reductant because it allows selective reactions, is cheap, and only produces CO2 as stoichiometric byproduct. However, the difficulty in handling pressurized CO has stimulated in recent years the development of CO‐surrogates, that is molecules able to liberate CO during the reaction. The use of phosphines and diols has also been developed in conjunction with molybdenum catalysts. The review focusses in more detail on the literature in the period 2006–2018, but reference to earlier work is made when necessary to put recent results in a more general context.

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“…Most condensed phase homoleptic transition metal carbonyl complexes and all neutral mononuclear homoleptic transition metal carbonyl complexes in particular, obey the 18-electron rule 7 ; the only exception is V(CO) 6 as a 17 valence electron (VE) species. Neutral complexes can be reduced to gain anionic carbonyl metallates, such as [V(CO) 6 ] − , [Fe(CO) 4 ] 2− (discovered as early as 1930) or even clustered radical anions such as [Fe 3 (CO) 11 ] •− 8,9 . Transition metal carbonyl cations (TMCCs), however, could not be accessed until about 1960, when the octahedral carbonyl cation [Mn(CO) 6 ] + was discovered 10 .…”

Section: Introductionmentioning

confidence: 99%

Stable salts of the hexacarbonyl chromium(I) cation and its pentacarbonyl-nitrosyl chromium(I) analogue

et al. 2019

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Homoleptic carbonyl radical cations are a textbook family of complexes hitherto unknown in the condensed phase, leaving their properties and applications fundamentally unexplored. Here we report on two stable 17-electron [Cr(CO)6]•+ salts that were synthesized by oxidation of Cr(CO)6 with [NO]+[Al(ORF)4]− (RF = C(CF3)3)) in CH2Cl2 and with removal of NO gas. Longer reaction times led to NO/CO ligand exchange and formation of the thermodynamically more stable 18-electron species [Cr(CO)5(NO)]+, which belongs to the family of heteroleptic chromium carbonyl/nitrosyl cations. All salts were fully characterized (IR, Raman, EPR, NMR, scXRD, pXRD, magnetics) and are stable at room temperature under inert conditions over months. The facile synthesis of these species enables the thorough investigation of their properties and applications to a broad scientific community.

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Radical Processes in the Reduction of Nitrobenzene Promoted by Iron Carbonyl Clusters. X-ray Crystal Structures of [Fe3(CO)9(.mu.3-NPh)]2-, [HFe3(CO)9(.mu.3-NPh)]-, and the Radical Anion [Fe3(CO)11]-.bul.

Cited by 58 publications

References 0 publications

Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt₃₃(CO)₃₈]^2– and the bcc [Pt₄₀(CO)₄₀]^6– Molecular Nanoclusters

Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt₃₃(CO)₃₈]^2– and the bcc [Pt₄₀(CO)₄₀]^6– Molecular Nanoclusters

Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

Stable salts of the hexacarbonyl chromium(I) cation and its pentacarbonyl-nitrosyl chromium(I) analogue

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Radical Processes in the Reduction of Nitrobenzene Promoted by Iron Carbonyl Clusters. X-ray Crystal Structures of [Fe3(CO)9(.mu.3-NPh)]2-, [HFe3(CO)9(.mu.3-NPh)]-, and the Radical Anion [Fe3(CO)11]-.bul.

Cited by 58 publications

References 0 publications

Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt33(CO)38]2– and the bcc [Pt40(CO)40]6– Molecular Nanoclusters

Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt33(CO)38]2– and the bcc [Pt40(CO)40]6– Molecular Nanoclusters

Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

Stable salts of the hexacarbonyl chromium(I) cation and its pentacarbonyl-nitrosyl chromium(I) analogue

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Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt₃₃(CO)₃₈]^2– and the bcc [Pt₄₀(CO)₄₀]^6– Molecular Nanoclusters

Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt₃₃(CO)₃₈]^2– and the bcc [Pt₄₀(CO)₄₀]^6– Molecular Nanoclusters