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 12 publications

(1 citation statement)

References 69 publications

(58 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

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

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

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

et al. 2017

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Bimetallic Fe–Cu Carbido Carbonyl Clusters Obtained from the Reactions of [Fe4C(CO)12{Cu(MeCN)}2] with N-Donor Ligands

et al. 2015

View full text Add to dashboard Cite

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

Cited by 12 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)]⁺

Bimetallic Fe–Cu Carbido Carbonyl Clusters Obtained from the Reactions of [Fe4C(CO)12{Cu(MeCN)}2] with N-Donor Ligands

Contact Info

Product

Resources

About

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

Cited by 12 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)]+

Bimetallic Fe–Cu Carbido Carbonyl Clusters Obtained from the Reactions of [Fe4C(CO)12{Cu(MeCN)}2] with N-Donor Ligands

Contact Info

Product

Resources

About

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