A Comparative Experimental and Computational Study of Heterometallic Fe‐M (M = Cu, Ag, Au) Carbonyl Clusters Containing N‐Heterocyclic Carbene Ligands

Berti, Beatrice; Bortoluzzi, Marco; Cesari, Cristiana; Femoni, Cristina; Iapalucci, Maria Carmela; Mazzoni, Rita; Zacchini, Stefano

doi:10.1002/ejic.202000260

Cited by 15 publications

(14 citation statements)

References 63 publications

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“…It is composed by an Ag 2 unit bonded to two terminal (Co t ) and two edge bridging (Co b ) Co(CO) 4 units. The Ag-Ag contact is slightly different in the four salts (2.8425(3) Å for Na 2 ( 5 )·C 4 H 6 O 2 , 2.8775(7) Å for [PPN] 2 ( 5 )·C 5 H 12 , 2.91970(17) Å for [NBu 4 ] 2 ( 5 ), 2.916(4) and 2.923(4) Å for [NMe 4 ] 2 ( 5 )) and is indicative of an argentophilic interaction as found in other Ag clusters supported by organometallic carbonyl fragments [ 45 , 46 , 47 ]. As expected, the Co t -Ag contacts [2.6537(3), 2.6692(7), 2.67936(18), 2.669(4) and 2.679(4) Å for the four salts] are shorter than Co b -Ag [2.8576(3), 2.8094(10), 2.75393(19)–2.8475(2) and 2.787(4)–2.805(4) Å].…”

Section: Resultsmentioning

confidence: 86%

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: Resultsmentioning

confidence: 86%

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

et al. 2021

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“…[1a, 2b,4] So far, sterically demanding donor ligands,s uch as NHCs (Nheterocyclic carbenes) or phosphines,w ere applied for the isolation of these smallest units of the gold-iron alloy (Figure 1). [5] Siliconsa bility to partially mimic its lighter congener carbon, and to show metal-like behavior at the same time,has been ap owerful concept for small molecule activation and preparation of novel materials. [6] In recent years,silicon-based ligands beyond conventional silyl-ligands have been highlighted.…”

Section: Introductionmentioning

confidence: 99%

A Zwitterionic Heterobimetallic Gold–Iron Complex Supported by Bis(N‐Heterocyclic Imine)Silyliumylidene

et al. 2021

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The facile synthesis of the first bis‐N‐heterocyclic imine‐stabilized chlorosilyliumylidene 1 is reported. Remarkably, consecutive reaction of 1 with PPh3AuCl and K2Fe(CO)4 gives rise to the unique heterobimetallic complex 1,2‐(MesNHI)2‐C2H4‐ClSiAuFe(CO)4 (4). The overall neutral complex 4 bears an unusual linear Si−Au−Fe structure and a rare anagostic interaction between the d10‐configured gold atom and a CH bond of the mesityl ligand. According to the computational analysis and 57Fe Mössbauer spectroscopy, the formal Fe‐oxidation state remains at −II. Thus, the electronic structure of 4 is best described as an overall neutral—yet zwitterionic—heterobimetallic “Si(II)+‐Au(I)+‐Fe(‐II)2−”‐silyliumylidene complex, derived from double anion exchange. The computational analysis indicates strong hyperconjugative back donation from the gold(I) atom to the silyliumylidene ligand.

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“…The double functionalization with (NHC)M C Cl (M C = Cu, Ag, Au) has been possible using the unmodified Collman's reagent as the substrate (Scheme 44) [206][207][208][209][210]. For example, the reaction of Na 2 [Fe(CO) 4 ] with 2 eq.…”

Section: Reactions With the Formation Of Bimetallic Adducts Retaining The Nhc-m с Bondmentioning

confidence: 99%

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Mikhaylov

Балова

2021

Russ J Gen Chem

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The carbene transfer from N-heterocyclic carbene complexes of Group 11 metals (NHC-M C ) (especially silver and copper) to other metals is considered a convenient and universal, sometimes having no alternative, method for the synthesis of a wide range of important N-heterocyclic carbene complexes of transition metals. As the number of successful examples of transmetalation with the formation of the target product has increased, the data were accumulated on alternative or unexpected results of the interaction of NHC-M C complexes with compounds of other metals. This review considers the examples of NHC-M C reactions with compounds of other metals which proceed with a change in the metals oxidation state, conversion of (NHC)M C X into cationic homoleptic [(NHC) 2 M C ] + forms, transmetalation retaining the other metal in the coordination sphere of the product, or formation of heterometallic adducts preserving the M C -C carbene bond, rather than these occurring according to the standard reaction pathway. Unusual "reverse" carbene transfer reactions have been considered separately. The review material reveals a promising new synthetic potential of NHC-M C in the reactions with other metals and discusses the possible mechanisms and driving forces of such transformations. The most important aspects of the application of the obtained products, primarily in various catalytic processes, have been considered as well.

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A Comparative Experimental and Computational Study of Heterometallic Fe‐M (M = Cu, Ag, Au) Carbonyl Clusters Containing N‐Heterocyclic Carbene Ligands

Cited by 15 publications

References 63 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

A Zwitterionic Heterobimetallic Gold–Iron Complex Supported by Bis(N‐Heterocyclic Imine)Silyliumylidene

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

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