Co5C and Co4C carbido carbonyl clusters stabilized by [AuPPh3]+ fragments

Ciabatti, Iacopo; Femoni, Cristina; Hayatifar, Mohammad; Iapalucci, Maria Carmela; Zacchini, Stefano

doi:10.1016/j.ica.2015.01.032

Cited by 13 publications

(1 citation statement)

References 69 publications

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“…In addition, dynamic permutational isomerism was detected in the trigonal bypiramidal W 2 RhIr 2 (CO) 9 (η 5 -C 5 H 5 ) 2 (η 5 -C 5 HMe 4 ) cluster, resulting from competitive capping of either a W 2 Ir or WIr 2 face of the cluster [23]. Surface isomerism is well represented in Ni and Co carbide carbonyl clusters decorated by Au(PPh 3 ) fragments, such as Ni 6 C(CO) 9 (AuPPh 3 ) 4 [24], Co 5 C(CO) 11 (AuPPh 3 ) 3 [25] and Co 6 C(CO) 12 (AuPPh 3 ) 4 [26]. Four different isomers have been reported for [Ni 17 (C 2 ) 2 (CO) 24 ] 4− , in which a Ni(CO) fragment may cap the [Ni 16 (C 2 ) 2 (CO) 23 ] 4− core of the cluster in four different modes [27].…”

Section: Introductionmentioning

confidence: 99%

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

et al. 2021

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The reaction of [Co(CO)4]− (1) with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)4}2]− (M = Cu, 2; Ag, 3; Au, 4) were obtained by reacting 1 with M(I) in a 2:1 molar ratio. Their molecular structures were corroborated by single-crystal X-ray diffraction (SC-XRD) on isomorphous [NEt4][M{Co(CO)4}2] salts. [NEt4](3)represented the first structural characterization of 3. More interestingly, changing the crystallization conditions of solutions of 3, the hexanuclear cluster [Ag2{Co(CO)4}4]2− (5) was obtained in the solid state instead of 3. Its molecular structure was determined by SC-XRD as Na2(5)·C4H6O2, [PPN]2(5)·C5H12 (PPN = N(PPh3)2]+), [NBu4]2(5) and [NMe4]2(5) salts. 5 may be viewed as a dimer of 3 and, thus, it represents a rare case of polymerization isomerism (that is, two compounds having the same elemental composition but different molecular weights) in cluster chemistry. The phenomenon was further studied in solution by IR and ESI-MS measurements and theoretically investigated by computational methods. Both experimental evidence and density functional theory (DFT) calculations clearly pointed out that the dimerization process occurs in the solid state only in the case of Ag, whereas Cu and Au related species exist only as monomers.

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Section: Introductionmentioning

confidence: 99%

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

et al. 2021

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Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

et al. 2017

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The reduction of [Fe6C(CO)16]2– (1) with NaOH in DMSO or with Na/naphthalene in THF affords the highly reduced [Fe6C(CO)15]4– (2) monocarbide tetraanion. The molecular structure of 2 has been crystallographically determined as its [Et4N]4[Fe6C(CO)15]·CH3CN salt, revealing an octahedral structure as expected for a hexanuclear cluster possessing 86 valence electrons. The stepwise protonation of 2 with strong acids such as HBF4·Et2O results first in the monohydride trianion [HFe6C(CO)15]3– (3) and then the purported dihydride dianion [H2Fe6C(CO)15]2– (4), as indicated by 1H NMR spectroscopy. Both 3 and 4 are not stable enough to be isolated and rapidly decompose, yielding the parent dianion 1. The reaction of 2 with a slight excess of Au(PPh3)Cl affords the aurated dianion [Fe6C(CO)15(AuPPh3)2]2– (5), which has been isolated and structurally characterized as its [Et4N]2[Fe6C(CO)15(AuPPh3)2]·2CH3CN salt. DFT calculations allowed us to study, from a computational point of view, the electronic features of the new compounds and possible reaction intermediates.

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Isomerism in Molecular Metal Carbonyl Clusters

Cesari,

Femoni,

Forti

et al. 2024

Eur J Inorg Chem

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The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand‐protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M‐M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.

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Co5C and Co4C carbido carbonyl clusters stabilized by [AuPPh3]+ fragments

Cited by 13 publications

References 69 publications

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

Isomerism in Molecular Metal Carbonyl Clusters

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Co5C and Co4C carbido carbonyl clusters stabilized by [AuPPh3]+ fragments

Cited by 13 publications

References 69 publications

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

Synthesis of the Highly Reduced [Fe6C(CO)15]4– Carbonyl Carbide Cluster and Its Reactions with H+ and [Au(PPh3)]+

Isomerism in Molecular Metal Carbonyl Clusters

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Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺