Peraurated nickel carbide carbonyl clusters: the cationic [Ni6(C)(CO)8(AuPPh3)8]2+monocarbide and the [Ni12(C)(C2)(CO)17(AuPPh3)3]−anion containing one carbide and one acetylide unit

Bortoluzzi, Marco; Ciabatti, Iacopo; Femoni, Cristina; Hayatifar, Mohammad; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano

doi:10.1039/c4dt01849d

Cited by 16 publications

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“…The data herein reported confirm the ability of interstitial heteroatoms to increase the stability of metal carbonyl clusters, favoring the formation of higher nuclearity species. ,,− As a further consequence of this enhanced stability, large molecular metal carbonyl clusters containing interstitial heteroatoms are often multivalent and may display several reversible redox processes. This point is demonstrated by comparing the rich redox behavior of [H 6– n Ni 31 P 4 (CO) 39 ] n − ( n = 4,5) with the fact that in the case of [Ni 11 P(CO) 18 ] 3– spectroelectrochemical studies demonstrate only the reversible formation of the tetra-anion [Ni 11 P(CO) 18 ] 4– .…”

Section: Discussionsupporting

confidence: 72%

“…[Ni 31 Sb 4 (CO) 40 ] 6– is even more electron-rich, possessing 416 CVE (6n+22 CMO). Such rich electron counts are usual for large nickel carbonyl clusters containing several interstitial heteroatoms, as found in polycarbide nickel carbonyls. − …”

Section: Resultsmentioning

confidence: 93%

“…It has been pointed out that molecular metal nanoclusters might be interesting models for the investigation of metal aggregates at the nanolevel, as well as promising precursors for the preparation of metal nanoparticles and catalytic materials. − Thus, it is quite remarkable that molecular nickel phosphide nanoclusters have not been reported up to now. This should be contrasted with the tendency of Ni to form several molecular carbonyl clusters containing other fully interstitial p-block elements, such as C, Ga, Ge, Sn, and Sb. , Ni-carbide carbonyl clusters display a very rich chemistry and may contain 1–10 interstitial C atoms. − Conversely, heavier heteroatoms show a poorer chemistry. Ga, Ge, and Sn are limited to icosahedral Ni-carbonyl clusters containing a single fully interstitial heteroatom, , whereas [Ni 11 Bi 2 (CO) 18 ] 3– contains two semi-interstitial Bi-atoms .…”

Section: Introductionmentioning

confidence: 99%

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Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni₁₁P(CO)₁₈]^3–and [H_6–nNi₃₁P₄(CO)₃₉]ⁿ⁻(n= 4 and 5)

et al. 2018

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The reaction of [NEt][Ni(CO)] in thf with 0.5 equiv of PCl affords the monophosphide [NiP(CO)] that in turn further reacts with PCl resulting in the tetra-phosphide carbonyl cluster [HNiP(CO)]. Alternatively, the latter can be obtained from the reaction of [NEt][Ni(CO)] in thf with 0.8-0.9 equiv of PCl. The [HNiP(CO)] penta-anion is reversibly protonated by strong acids leading to the [HNiP(CO)] tetra-anion, whereas deprotonation affords the [NiP(CO)] hexa-anion. The latter is reduced with Na/naphthalene yielding the [NiP(CO)] hepta-anion. In order to shed light on the polyhydride nature and redox behavior of these clusters, electrochemical and spectroelectrochemical studies were carried out on [NiP(CO)], [HNiP(CO)], and [HNiP(CO)]. The reversible formation of the stable [NiP(CO)] tetra-anion is demonstrated through the spectroelectrochemical investigation of [NiP(CO)]. The redox changes of [HNiP(CO)] show features of chemical reversibility and the vibrational spectra in the ν region of the nine redox states of the cluster [HNiP(CO)] (n = 3-11) are reported. The spectroelectrochemical investigation of [HNiP(CO)] revealed the presence of three chemically reversible reduction processes, and the IR spectra of [HNiP(CO)] (n = 4-7) have been recorded. The different spectroelectrochemical behavior of [HNiP(CO)] and [HNiP(CO)] support their formulations as polyhydrides. Unfortunately, all the attempts to directly confirm their poly hydrido nature by H NMR spectroscopy failed, as previously found for related large metal carbonyl clusters. Thus, the presence and number of hydride ligands have been based on the observed protonation/deprotonation reactions and the spectroelectrochemical experiments. The molecular structures of the new clusters have been determined by single-crystal X-ray analysis. These represent the first examples of structurally characterized molecular nickel carbonyl nanoclusters containing interstitial phosphide atoms.

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Section: Discussionsupporting

confidence: 72%

Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

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Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni₁₁P(CO)₁₈]^3–and [H_6–nNi₃₁P₄(CO)₃₉]ⁿ⁻(n= 4 and 5)

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“…31 Conversely, [Ni 12 (C 2 )(C)(CO) 17 (AuPPh 3 ) 3 ] − presented one carbide and a C 2 -acetylide unit. 34…”

Section: Resultsmentioning

confidence: 99%

“…20,21,36 A related surface ligand isomerism has been documented also for organometallic nanoclusters, and in particular in the case of cobalt and nickel carbide carbonyl clusters decorated on the surface by [AuPPh 3 ] + fragments. 34,37,38…”

Section: Discussionmentioning

confidence: 99%

Cluster Core Isomerism Induced by Crystal Packing Effects in the [HCo₁₅Pd₉C₃(CO)₃₈]^2– Molecular Nanocluster

et al. 2018

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This article describes a rare case of cluster core isomerism in a large molecular organometallic nanocluster. In particular, two isomers of the [HCo 15 Pd 9 C 3 (CO) 38 ] 2– nanocluster, referred as TP-Pd 9 and Oh-Pd 9 , have been structurally characterized by single-crystal X-ray crystallography as their [NMe 3 (CH 2 Ph)] 2 [HCo 15 Pd 9 C 3 (CO) 38 ]·CH 2 Cl 2 (ca. 1:1 TP-Pd 9 and Oh-Pd 9 mixture), [NMe 3 (CH 2 Ph)] 2 [HCo 15 Pd 9 C 3 (CO) 38 ]·2CH 2 Cl 2 (mainly TP-Pd 9 ), [NEt 3 (CH 2 Ph)] 2 [HCo 15 Pd 9 C 3 (CO) 38 ]·CH 2 Cl 2 (mainly TP-Pd 9 ), [MePPh 3 ] 2 [HCo 15 Pd 9 C 3 (CO) 38 ]·2.5CH 2 Cl 2 (mainly TP-Pd 9 ), and [MePPh 3 ] 2 [HCo 15 Pd 9 C 3 (CO) 38 ] (Oh-Pd 9 ) salts. The cluster core of TP-Pd 9 is a tricapped trigonal prism, whereas this is a tricapped octahedron in Oh-Pd 9 . The presence in the solid state of the Oh-Pd 9 or TP-Pd 9 isomers depends on the cation employed and/or the number and type of co-crystallized solvent molecules. Often, mixtures of the two isomers, within the same single crystal or as mixtures of different crystals within the same crystallization batch, are obtained. Structural isomerism in organometallic nanoclusters is discussed and compared to that in Au–thiolate nanoclusters.

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Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

et al. 2017

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The reduction of [Fe6C(CO)16]2– (1) with NaOH in DMSO or with Na/naphthalene in THF affords the highly reduced [Fe6C(CO)15]4– (2) monocarbide tetraanion. The molecular structure of 2 has been crystallographically determined as its [Et4N]4[Fe6C(CO)15]·CH3CN salt, revealing an octahedral structure as expected for a hexanuclear cluster possessing 86 valence electrons. The stepwise protonation of 2 with strong acids such as HBF4·Et2O results first in the monohydride trianion [HFe6C(CO)15]3– (3) and then the purported dihydride dianion [H2Fe6C(CO)15]2– (4), as indicated by 1H NMR spectroscopy. Both 3 and 4 are not stable enough to be isolated and rapidly decompose, yielding the parent dianion 1. The reaction of 2 with a slight excess of Au(PPh3)Cl affords the aurated dianion [Fe6C(CO)15(AuPPh3)2]2– (5), which has been isolated and structurally characterized as its [Et4N]2[Fe6C(CO)15(AuPPh3)2]·2CH3CN salt. DFT calculations allowed us to study, from a computational point of view, the electronic features of the new compounds and possible reaction intermediates.

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Peraurated nickel carbide carbonyl clusters: the cationic [Ni₆(C)(CO)₈(AuPPh₃)₈]²⁺monocarbide and the [Ni₁₂(C)(C₂)(CO)₁₇(AuPPh₃)₃]⁻anion containing one carbide and one acetylide unit

Cited by 16 publications

References 77 publications

Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni₁₁P(CO)₁₈]^3–and [H_6–nNi₃₁P₄(CO)₃₉]ⁿ⁻(n= 4 and 5)

Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni₁₁P(CO)₁₈]^3–and [H_6–nNi₃₁P₄(CO)₃₉]ⁿ⁻(n= 4 and 5)

Cluster Core Isomerism Induced by Crystal Packing Effects in the [HCo₁₅Pd₉C₃(CO)₃₈]^2– Molecular Nanocluster

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

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Peraurated nickel carbide carbonyl clusters: the cationic [Ni6(C)(CO)8(AuPPh3)8]2+monocarbide and the [Ni12(C)(C2)(CO)17(AuPPh3)3]−anion containing one carbide and one acetylide unit

Cited by 16 publications

References 77 publications

Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni11P(CO)18]3–and [H6–nNi31P4(CO)39]n−(n= 4 and 5)

Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni11P(CO)18]3–and [H6–nNi31P4(CO)39]n−(n= 4 and 5)

Cluster Core Isomerism Induced by Crystal Packing Effects in the [HCo15Pd9C3(CO)38]2– Molecular Nanocluster

Synthesis of the Highly Reduced [Fe6C(CO)15]4– Carbonyl Carbide Cluster and Its Reactions with H+ and [Au(PPh3)]+

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Peraurated nickel carbide carbonyl clusters: the cationic [Ni₆(C)(CO)₈(AuPPh₃)₈]²⁺monocarbide and the [Ni₁₂(C)(C₂)(CO)₁₇(AuPPh₃)₃]⁻anion containing one carbide and one acetylide unit

Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni₁₁P(CO)₁₈]^3–and [H_6–nNi₃₁P₄(CO)₃₉]ⁿ⁻(n= 4 and 5)

Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni₁₁P(CO)₁₈]^3–and [H_6–nNi₃₁P₄(CO)₃₉]ⁿ⁻(n= 4 and 5)

Cluster Core Isomerism Induced by Crystal Packing Effects in the [HCo₁₅Pd₉C₃(CO)₃₈]^2– Molecular Nanocluster

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺