New examples of the metal basicity of iron pentacarbonyl

Dean, Philip A. W.; Ibbott, David G.; Bancroft, G. M.

doi:10.1039/c39760000901

Cited by 9 publications

(7 citation statements)

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“…A more recent family of cationic multinuclear TMCs are the Lewis adducts of neutral TMCs with coinage metal(I) cations, which led to the cationic heterotrinuclear TMC clusters [M{Fe(CO) 5 } 2 ] + (M=Cu, Ag, Au) and [Ag({M’(CO) 6 } 2 ] + (M’=Mo, W) [6,7,8] . In addition, a dicationic Cd 2+ adduct [Cd{Fe(CO) 5 } 2 ] 2+ is known [9] . Moreover, anionic TMCs like [M(CO) 6 ] – (M=Nb, Ta) as ligands induced clustering with Ag + ions in rather large cationic heterobimetallic clusters, i. e. in super‐tetrahedral [Ag 6 (M(CO 6 ) 4 ] 2+ [10] …”

Section: Introductionmentioning

confidence: 99%

“…[6,7,8] In addition, a dicationic Cd 2 + adduct [Cd{Fe(CO) 5 } 2 ] 2 + is known. [9] Moreover, anionic TMCs like [M(CO) 6 ] -(M=Nb, Ta) as ligands induced clustering with Ag + ions in rather large cationic heterobimetallic clusters, i. e. in super-tetrahedral [Ag 6 (M(CO 6 ) 4 ] 2 + . [10] Genuinely inspired by the TMCs, Nobel laureate R. Hoffmann introduced the concept of isolobal analogies, where he compared for example the •Re(CO) 5 fragments in Re 2 (CO) 10 to the methyl radical (a pseudo-halogen), the Os(CO) 4 fragments in Os 3 (CO) 12 to a methylene unit (a pseudo-chalcogen) and the Ir(CO) 3 fragments in Ir 4 (CO) 12 to the methylidyne moiety (a pseudo-pnictogen).…”

Section: Introductionmentioning

confidence: 99%

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Coordination versus Insertion: On the Interaction of 5 d‐Transition Metal Carbonyl Clusters with Silver(I)

Sellin

Seiler

Krossing

2023

Chemistry A European J

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The title silver(I) complex salts [Ag{Re2(CO)10}{Re(CO)5}2]+[Al(ORF)4]− (AgRe4; ORF=‐OC(CF3)3) and [Ag{Ir4(CO)12}2]+[Al(ORF)4]− (AgIr8) form upon reaction of Ag+[Al(ORF)4]− and the transition metal carbonyls (TMCs) Re2(CO)10 and Ir4(CO)12 respectively. The solid‐state structure of the AgRe4 cluster shows an unexpected asymmetric coordination motif, wherein the silver(I) cation has inserted into the Re−Re bond of one Re2(CO)10 moiety, while the other dirhenium carbonyl coordinates only over one metal atom towards the silver(I) cation. The AgIr8 cluster is formed by the edge‐on coordination of two Ir4 tetrahedra and the silver cation in a D2 symmetric fashion with a torsion angle of 46.5°. QTAIM analysis shows bond paths between the silver atom and the nearby metal atoms in all cases, whereas only the non‐inserted Re2(CO)10 moiety shows additional bond paths between the carbonyl ligands and the silver cation. In addition, the insertion of the Ag+ cation into the Re−Re bond in Re2(CO)10 removes the bond path between the two rhenium atoms. The EDA‐NOCV analysis suggests an increase of the interaction energy between the silver(I) cation and the respective metal carbonyls from the metal centered transition metal carbonyl (TMC) donors W(CO)6

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Coordination versus Insertion: On the Interaction of 5 d‐Transition Metal Carbonyl Clusters with Silver(I)

Sellin

Seiler

Krossing

2023

Chemistry A European J

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“…16 In comparison, the corresponding group 12 chemistry has received very little attention and no structurally characterized metal complexes with Fe(CO) 5 ligands exist. 19 However, adducts of Fe(CNR) 5 to Hg(II) have been reported. 20 Due to our recent interest in mercury chemistry, 21,22 we wondered whether Hg(II) compounds could form isolable complexes with Fe(CO) 5 as a ligand.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In comparison, the corresponding group 12 chemistry has received very little attention and no structurally characterized metal complexes with Fe(CO) 5 ligands exist . However, adducts of Fe(CNR) 5 to Hg(II) have been reported .…”

Section: Introductionmentioning

confidence: 99%

Structural Characterization and Bonding Analysis of [Hg{Fe(CO)₅}₂]²⁺ [SbF₆]⁻₂

et al. 2023

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The non-classical carbonyl complex [Hg{Fe(CO)5}2]2+ [SbF6]− 2 is prepared by reaction of Hg(SbF6)2 and excess Fe(CO)5 in anhydrous HF. The single-crystal X-ray structure reveals a linear Fe–Hg–Fe moiety as well as an eclipsed conformation of the eight basal CO ligands. Interestingly, the Hg–Fe bond length of 2.5745(7) Å is relatively similar to the corresponding Hg–Fe bonds in literature-known [Hg{Fe(CO)4}2]2– dianions (2.52–2.55 Å), which intrigued us to analyze the bonding situation in both the dications and dianions with the energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV) method. Both species are best described as Hg(0) compounds, which are also confirmed by the shape of the HOMO-4 and HOMO-5 of the dication and dianion, respectively, in which the electron pair is located mainly at the Hg. Furthermore, for the dication and the dianion, the σ back-donation from Hg into the [Fe(CO)5]2 2+ or the [Fe(CO)4]2 2– fragment is the most dominant orbital interaction and surprisingly these interaction energies are also very similar even in absolute values. The fact that both iron-based fragments are missing two electrons explains their prominent σ-acceptor properties.

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“…, catalysis, luminescence), 2 as well as due to their relevance in biology. 3 Among these, coinage metal (Cu, Ag, Au) complexes of Fe(CO) 5 are of particular interest to us, 4 not only because they are heterometallic species but also feature an interesting and rarely exploited organometallic ligand 5 with a long history (in fact, Fe(CO) 5 was first reported in 1891). 1 a ,6 Its chemistry with Lewis bases such as isocyanides and phosphines leading to CO substitution, in contrast, is well-known.…”

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confidence: 99%