Molecular Fe, CO and Ni carbide carbonyl clusters and Nanoclusters†

Cesari, Cristiana; Femoni, Cristina; Iapalucci, Maria Carmela; Zacchini, Stefano

doi:10.1016/j.ica.2022.121235

Cited by 5 publications

(10 citation statements)

References 109 publications

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“…Further details can be found in the literature. 26,28,29,31,39,43,44,49,51 The structure of [HPt 14+x Ni 24−x (CO) 44 ] 5− (x = 0.70) consists of a truncated-ν 3 -octahedron (truncated octahedron of frequency three) as also found in the metal core of [Pt 38 (CO) 44 ] 2− . 48 The ccp M 44 and the two apexes of the pentagonal pyramids (5 M-M contacts, 1 terminal CO), whereas the 10 positions within the external pentagons (5 M-M contacts, 1 terminal and 1 μ-CO) are disordered Pt/Ni.…”

Section: Dalton Transactionsmentioning

confidence: 99%

“…26,28,29,31,39,43,44,49,51 The structure of [HPt 14+x Ni 24−x (CO) 44 ] 5− (x = 0.70) consists of a truncated-ν 3 -octahedron (truncated octahedron of frequency three) as also found in the metal core of [Pt 38 (CO) 44 ] 2− . 48 The ccp M 44 and the two apexes of the pentagonal pyramids (5 M-M contacts, 1 terminal CO), whereas the 10 positions within the external pentagons (5 M-M contacts, 1 terminal and 1 μ-CO) are disordered Pt/Ni. Regarding the two apexes of the two pentagonal pyramids it is likely that Ni is too small in order to cap a pentagonal M 5 face and, thus, also these positions are occupied by Pt.…”

Section: Dalton Transactionsmentioning

confidence: 99%

“…The problems related to the assignment of the number of hydrides and their location within metal carbonyl clusters of increasing sizes have been previously discussed. 28,29,31,39,43,44 In the case of lower nuclearity metal carbonyl clusters (that is, those with up to 20-25 metal atoms), the presence of H-atoms, their number and often also their location can be inferred from 1 H NMR spectroscopy and SC-XRD analyses. In some fortunate cases, e.g.…”

Section: Introductionmentioning

confidence: 99%

“…Nonetheless, SC-XRD studies give a direct evidence of the charge of the cluster anion, by counting the number of counterions. If two clusters have the same structure (excluding H-atoms) and different charges, there are two possibilities: 21,43,44 (1) They are the same species with a different oxidation state. In this case, the cyclic voltammetric (CV) profiles of the two differently charged anion should be identical, being the same species with a different oxidation state.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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From M₆ to M₁₂, M₁₉ and M₃₈ molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

et al. 2023

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Section: Dalton Transactionsmentioning

confidence: 99%

Section: Dalton Transactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

From M₆ to M₁₂, M₁₉ and M₃₈ molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

et al. 2023

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Mechanistic Insights into ZIF-8 Encapsulation of Atom-Precise Pt(M) Carbonyl Clusters

et al. 2023

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Precisely designing metal nanoparticles (NPs) is the cornerstone for maximizing their efficiency in applications like catalysis or sensor technology. Metal–organic frameworks (MOFs) with their defined and tunable pore systems provide a confined space to host and stabilize small metal NPs. In this work, the MOF encapsulation of various atom-precise clusters following the bottle-around-ship approach is investigated, providing general insights into the scaffolding mechanism. Eleven carbonyl-stabilized Pt(M) (M = Co, Ni, Fe, and Sn) clusters are employed for the encapsulation in the zeolitic imidazolate framework (ZIF)-8. Infrared and UV/Vis spectroscopy, density functional theory, and ab initio molecular dynamics revealed structure–encapsulation relationship guidelines. Thereby, cluster polarization, size, and composition were found to condition the scaffolding behavior. Encaging of [NBnMe3]2[Co8Pt4C2(CO)24] (Co8Pt4 ) is thus achieved as the first MOF-encapsulated bimetallic carbonyl cluster, Co8Pt4 @ZIF-8, and is fully characterized including X-ray absorption near edge and extended X-ray absorption spectroscopy. ZIF-8 confinement not only promotes property changes, like the T-dependent magnetism, but it also further allows heat-induced ligand-stripping without altering the cluster size, enabling the synthesis of naked, heterometallic, close to atom-precise clusters.

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Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru₆C(CO)₁₅]^4–

Cesari,

Bortoluzzi,

Funaioli

et al. 2023

Inorg. Chem.

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The reaction of [Ru 6 C(CO) 16 ] 2– ( 1 ) with NaOH in DMSO resulted in the formation of a highly reduced [Ru 6 C(CO) 15 ] 4– ( 2 ), which was readily protonated by acids, such as HBF 4 ·Et 2 O, to [HRu 6 C(CO) 15 ] 3– ( 3 ). Oxidation of 2 with [Cp 2 Fe][PF 6 ] or [C 7 H 7 ][BF 4 ] in CH 3 CN resulted in [Ru 6 C(CO) 15 (CH 3 CN)] 2– ( 5 ), which was quantitatively converted into 1 after exposure to CO atmosphere. The reaction of 2 with a mild methylating agent such as CH 3, I afforded the purported [Ru 6 C(CO) 14 (COCH 3 )] 3– ( 6 ). By employing a stronger reagent, that is, CF 3 SO 3 CH 3 , a mixture of [HRu 6 C(CO) 16 ] − ( 4 ), [H 3 Ru 6 C(CO) 15 ] − ( 7 ), and [Ru 6 C(CO) 15 (CH 3 CNCH 3 )] − ( 8 ) was obtained. The molecular structures of 2–5 , 7 , and 8 were determined by single-crystal X-ray diffraction as their [NEt 4 ] 4 [ 2 ]·CH 3 CN, [NEt 4 ] 3 [ 3 ], [NEt 4 ][ 4 ], [NEt 4 ] 2 [ 5 ], [NEt 4 ][ 7 ], and [NEt 4 ][ 8 ]·solv salts. The carbyne–carbide cluster 6 was partially characterized by IR spectroscopy and ESI-MS, and its structure was computationally predicted using DFT methods. The redox behavior of 2 and 3 was investigated by electrochemical and IR spectroelectrochemical methods. Computational studies were performed in order to unravel structural and thermodynamic aspects of these octahedral Ru–carbide carbonyl clusters...

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Molecular Fe, CO and Ni carbide carbonyl clusters and Nanoclusters†

Cited by 5 publications

References 109 publications

From M₆ to M₁₂, M₁₉ and M₃₈ molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

From M₆ to M₁₂, M₁₉ and M₃₈ molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

Mechanistic Insights into ZIF-8 Encapsulation of Atom-Precise Pt(M) Carbonyl Clusters

Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru₆C(CO)₁₅]^4–

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Molecular Fe, CO and Ni carbide carbonyl clusters and Nanoclusters†

Cited by 5 publications

References 109 publications

From M6 to M12, M19 and M38 molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

From M6 to M12, M19 and M38 molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

Mechanistic Insights into ZIF-8 Encapsulation of Atom-Precise Pt(M) Carbonyl Clusters

Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru6C(CO)15]4–

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From M₆ to M₁₂, M₁₉ and M₃₈ molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

From M₆ to M₁₂, M₁₉ and M₃₈ molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru₆C(CO)₁₅]^4–