The possible role of metal carbonyl clusters in nanoscience and nanotechnologies

Femoni, Cristina; Iapalucci, Maria Carmela; Kaswalder, Francesco; Longoni, Giuliano; Zacchini, Stefano

doi:10.1016/j.ccr.2006.03.011

Cited by 168 publications

(235 citation statements)

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“…In doing that, a look to related behaviour of ligandstabilised and ligand-free clusters (Figure 9), including almost mono-dispersed ligand-stabilised metal nanoparticles, should be done. They found contribution of metal carbonyl clusters to some aspects of nanoscience and nanotechnologies also [237]. An approach to noble metal-metal oxide dumbbell nanoparticles based on seed-mediated growth ( Figure 10).…”

Section: In Nano Science and Nanotechnologiesmentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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KEYWORDSThe special interest attached to the chemistry of metal carbonyls arises from several causes. While quite distinct from the metal carbonyls in the organometallic compounds, they differ in physical properties (e.g., their volatility) from all other compounds of the transition metals. Chemically, they constitute a group of compounds in which the formal valency of the metal atoms is zero, and in this respect (apart, perhaps, from the ammoniates of the alkali metals) they are comparable only with the recently discovered compounds. As a class, the carbonyls are reactive compounds, and a number of new types of inorganic compounds have been discovered. In the concepts for new products, performance, product safety, and product economy criteria are equally important. They are taken into account already when the raw material base for a new industrial product development is defined. Since the discovery of nickel carbonyl by Mond and Langer in 1888, the carbonyls of the iron group and of chromium, molybdenum and tungsten have found important technical applications, e.g., in the Mond nickel process, and for the preparation of the metals in a state of subdivision and of purity suitable for powder metallurgy, for catalysts, etc. The reaction mechanism of the processes developed for producing the carbonyls technically has only recently received its interpretations. Within the space of review it is necessary to limit discussion to a few topics. Particular stress has accordingly laid upon (a) the chemical bonding in metal carbonyls, (b) importance of IR and NMR spectroscopy in characterization of metal carbonyls, (c) substitution reactions of G-VIb metal carbonyls, (d) kinetics and mechanism of substitution reactions in metal carbonyls, (e) substituted complexes of G-VIb metal carbonyl, (f) chelate complexes of G-VIb metal carbonyls, (g) uses of G-VIb metal carbonyl complexes and (h) studies done on G-VIb metal carbonyls.

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Section: In Nano Science and Nanotechnologiesmentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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“…Among transition metal carbonyls, these neutral Pd n (CO) x (PR 3 ) y clusters and their heterometallic derivatives are particularly remarkable in terms of their exceptional range in metal nuclearity (crystallographically varying from n = 3 to 165) and the unusual diversity of their structural types. Since the last superb review (Femoni et al 2006), indicating the possible contribution of high-nuclearity metal carbonyl clusters in nanoscience and nanotechnologies, the number of palladium clusters has considerably expanded to include the following new members that possess one or more interstitial metal atoms: Pd 37 (CO) 28 {P(p-Tolyl) 3 (a) Syntheses of homopalladium Pd n (CO) x (PR 3 ) y , n ≤ 10, via reduction of…”

Section: Introductionmentioning

confidence: 99%

Syntheses, structures and properties of primarily nanosized homo/heterometallic palladium CO/PR ₃ -ligated clusters

Mednikov

Dahl

2010

Phil. Trans. R. Soc. A.

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Syntheses, properties and structures of nanosized palladium CO/PR 3 -ligated homoand heterometallic clusters containing up to 165 metal atoms are the focus of this review. The work discussed is primarily that of the authors and their coworkers. We propose that the unparalleled variety of structural types and the distinctive reactivities of neutral Pd n (CO) x (PR 3 ) y clusters composed of zerovalent Pd atoms are a consequence of relatively weak Pd-L(ligand) and Pd(0)-Pd(0) interactions that result from the stable 5s 0 4d 10 closed-shell electron configuration of atomic Pd in its ground state.

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“…Given the complexity of such clusters, the agreement between the observed and calculated electron counts was remarkably good even for the highest nuclearity cluster, which was the 44-metal-atom [Ni 38 Pt 6 (CO) 48 H n ] n− (see the Ni 38 Pt 6 core in 34) at that time. 51 The observation that such large clusters conform to this simple electron counting suggested for a while that such species were attaining stable closedshell electronic configurations and therefore were molecules (with substantial HOMO -LUMO gaps) rather than metals in miniature (no HOMO -LUMO gap). These conclusions have somewhat been reconsidered later, with the study of their redox properties 51 and the characterization of new transitionmetal clusters of even larger nuclearity, especially ligated palladium-based nanosized clusters.…”

Section: Computational Methods: Transition Metal Clusters 13mentioning

confidence: 93%

“…51 The observation that such large clusters conform to this simple electron counting suggested for a while that such species were attaining stable closedshell electronic configurations and therefore were molecules (with substantial HOMO -LUMO gaps) rather than metals in miniature (no HOMO -LUMO gap). These conclusions have somewhat been reconsidered later, with the study of their redox properties 51 and the characterization of new transitionmetal clusters of even larger nuclearity, especially ligated palladium-based nanosized clusters. 52 Application of the Mingos high-nuclearity and condensation electron counting rules, 3 even to large complicated clusters, often give electron counts equal or close to the observed electron counts.…”

Section: Computational Methods: Transition Metal Clusters 13mentioning

confidence: 93%

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Computational Methods: Transition Metal Clusters

Gautier¹,

Halet²,

Saillard³

2005

Encyclopedia of Inorganic Chemistry

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Cluster chemistry is dominated by structural aspects. Indeed, structure and bonding are strongly related to stability and properties, and cluster structures are particularly diverse and often complex. Thus, electron‐counting rules, which relate structure to electron count, have been the key to the development of cluster chemistry as a distinct area of chemistry. These rules have been set up progressively along time with the help of quantum chemistry. This article deals with the recent progress on transition metal and mixed main group/transition metal cluster chemistry arising from the contribution of modern computational theory to the rationalization of structures. This article focuses on “viable” species, i.e., molecules that are isolable under reasonable conditions and deals with the exploration of the limitations of the classical electron‐counting rules as well as the establishment of new rules for new structural types with the help of quantum chemical calculations.

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The possible role of metal carbonyl clusters in nanoscience and nanotechnologies

Cited by 168 publications

References 207 publications

The chemistry of group-VIb metal carbonyls

The chemistry of group-VIb metal carbonyls

Syntheses, structures and properties of primarily nanosized homo/heterometallic palladium CO/PR ₃ -ligated clusters

Computational Methods: Transition Metal Clusters

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The possible role of metal carbonyl clusters in nanoscience and nanotechnologies

Cited by 168 publications

References 207 publications

The chemistry of group-VIb metal carbonyls

The chemistry of group-VIb metal carbonyls

Syntheses, structures and properties of primarily nanosized homo/heterometallic palladium CO/PR 3 -ligated clusters

Computational Methods: Transition Metal Clusters

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Syntheses, structures and properties of primarily nanosized homo/heterometallic palladium CO/PR ₃ -ligated clusters