Molecular nickel poly-carbide carbonyl nanoclusters: The octa-carbide [HNi42C8(CO)44(CuCl)]7– and the deca-carbide [Ni45C10(CO)46]6–

Bernardi, Alessandro; Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano

doi:10.1016/j.jorganchem.2015.09.013

Cited by 12 publications

(10 citation statements)

References 75 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…143 The largest Ni carbonyl cluster contains ten interstitial carbon atoms per 45 Ni (Figure 15 and Table 3). 144 Not only single carbides but also C 2 groups can be included into the metal core. 3).…”

Section: Giant Clusters With Compact Metallic Corementioning

confidence: 99%

See 1 more Smart Citation

Structural Chemistry of Giant Metal Based Supramolecules

2021

View full text Add to dashboard Cite

The review presents a bird-eye view on the state of research in the field of giant nonbiological discrete metal complexes and ions of nanometer size, which are structurally characterized by means of single-crystal X-ray diffraction, using the crystal structure as a common key feature. The discussion is focused on the main structural features of the metal clusters, the clusters containing compact metal oxide/hydroxide/chalcogenide core, ligand-based metal–organic cages, and supramolecules as well as on the aspects related to the packing of the molecules or ions in the crystal and the methodological aspects of the single-crystal neutron and X-ray diffraction of these compounds.

show abstract

Section: Giant Clusters With Compact Metallic Corementioning

confidence: 99%

“…Figure 15. (a) [Ni 45 C 10 (CO) 46 ] 6− cluster anion and close environment of the interstitial C atoms: (b) octahedral, (c) trigonal prismatic, and (d) monocapped trigonal prismatic 144. …”

mentioning

confidence: 99%

Structural Chemistry of Giant Metal Based Supramolecules

2021

View full text Add to dashboard Cite

show abstract

“…Conversely, by considering the two exposed P atoms contributing with only three electrons to the electron count, the cluster possesses 308 CVEs and 6 n + 22 CMOs. In both cases, [Ni 22 P 6 (CO) 30 ] 2– is rather electron rich, as often found in larger Ni carbonyl clusters containing several interstitial heteroatoms. − Indeed, the electron count of Ni–P carbonyl clusters seems to increase considerably by increasing the number of P atoms, that is, [Ni 11 P(CO) 18 ] 3– (6 n + 11), [Ni 14 P 2 (CO) 22 ] 2– (6 n + 14), [Ni 23– x P 2 (CO) 29– x ] 4– (6 n + 14), [Ni 39 P 3 (CO) 44 ] 6– (6 n + 16), [HNi 31 P 4 (CO) 34 ] 5– (6 n + 21), and [Ni 22 P 6 (CO) 30 ] 2– (6 n + 22 or 6 n + 24).…”

Section: Resultsmentioning

confidence: 89%

“…The sizes of the metal cores of these clusters range from 0.59 to 1.10 nm, and their overall dimensions including the CO ligands are 1.16–1.63 nm (Table ). Thus, the sizes of these molecular clusters are comparable to those of ultrasmall metal nanoparticles, molecular nanoclusters, or atomically precise metal nanoparticles. − In this respect, interstitial phosphide atoms seem to be as effective as carbides in order to stabilize molecular nickel carbonyl nanoclusters. − , …”

Section: Discussionmentioning

confidence: 99%

“…59−61 In this respect, interstitial phosphide atoms seem to be as effective as carbides in order to stabilize molecular nickel carbonyl nanoclusters. [42][43][44][45]59 The environment of the P atoms within these molecular Ni−P−CO nanoclusters displays a rich diversity. Indeed, they may be fully interstitial, semiexposed, or exposed in very diverse cages, that is, Ni 5 P pentagonal pyramid (exposed P in a pentagonal face), (highly distorted) Ni 7 P monocapped trigonal prism (semiexposed P), Ni 8 P bicapped trigonal prism, Ni 9 P monocapped square antiprism, Ni 10 P sphenocorona, Ni 10 P bicapped square antiprism, and Ni 12 P icosahedron (Figure 12).…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Structural Diversity in Molecular Nickel Phosphide Carbonyl Nanoclusters

et al. 2020

Self Cite

View full text Add to dashboard Cite

The reaction of [Ni6(CO)12]2– as a [NBu4]+ salt in CH2Cl2 with 0.8 equiv of PCl3 afforded [Ni14P2(CO)22]2–. In contrast, the reactions of [Ni6(CO)12]2– as a [NEt4]+ salt with 0.4–0.5 equiv of POCl3 afforded [Ni22–x P2(CO)29–x ]4– (x = 0.84) or [Ni39P3(CO)44]6– by using CH3CN and thf as a solvent, respectively. Moreover, by using 0.7–0.9 mol of POCl3 per mole of [NEt4]2[Ni6(CO)12] both in CH3CN and thf, [Ni23–x P2(CO)30–x ]4– (x = 0.82) was obtained together with [Ni22P6(CO)30]2– as a side product. [Ni23–x P2(CO)30–x ]4– (x = 0.82) and [Ni22P6(CO)30]2– were separated owing to their different solubility in organic solvents. All the new molecular nickel phosphide carbonyl nanoclusters were structurally characterized through single crystal X-ray diffraction (SC-XRD) as [NBu4]2[Ni14P2(CO)22] (two different polymorphs, P21/n and C2/c), [NEt4]4[Ni23–x P2(CO)30–x ]·CH3COCH3·solv (x = 0.82), [NEt4]2[Ni22P6(CO)30]·2thf, [NEt4]4[Ni22–x P2(CO)29–x ]·2CH3COCH3( x = 0.84) and [NEt4]6[Ni39P3(CO)44]·C6H14·solv. The metal cores’ sizes of these clusters range from 0.59 to 1.10 nm, and their overall dimensions including the CO ligands are 1.16–1.63 nm. In this respect, they are comparable to ultrasmall metal nanoparticles, molecular nanoclusters, or atomically precise metal nanoparticles. The environment of the P atoms within these molecular Ni–P–CO nanoclusters displays a rich diversity, that is, Ni5P pentagonal pyramid, Ni7P monocapped trigonal prism, Ni8P bicapped trigonal prism, Ni9P monocapped square antiprism, Ni10P sphenocorona, Ni10P bicapped square antiprism, and Ni12P icosahedron.

show abstract