Platinum Carbonyl Clusters Chemistry: Four Decades of Challenging Nanoscience

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

doi:10.1007/s10876-013-0639-3

Cited by 70 publications

(90 citation statements)

References 97 publications

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“…As ten 5s combinations are actually occupied in the dianionic clusters, it means that nine 4d-type combinations have formally transferred their electrons to nine of the 5s combinations. To get a deeper understanding on this molecular orbital (MO) level crossing, we used the opportunity given by the ADF program suite to express the molecular orbitals as linear combinations of the orbitals of two fragments, that we chose to be the [Pd 55 ] 2À metal kernel and its complete [(CO) 32 ] ligand shell, respectively. Unsurprisingly, single-point spin-restricted calculations (as required by the ADF program) on the [Pd 55 ] 2À fragment could not be converged in a reasonable ground state.…”

Section: Resultsmentioning

confidence: 99%

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Theoretical Analysis of the Mackay Icosahedral Cluster Pd₅₅(PiPr₃)₁₂(μ₃‐CO)₂₀: An Open‐Shell 20‐Electron Superatom

Wei

Marchal

Astruc

et al. 2020

Chemistry A European J

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The electronic structure of the spherical Mackay icosahedral nanosized cluster Pd 55 (PiPr 3 ) 12 (m 3 -CO) 20 is analyzed by using DFT calculations. Results reveal that it can be considered as a regular superatom with a "magic" electron count of 20, characterized by a 1S 2 1P 6 1D 10 2S 2 jellium configuration. Its open shell nature is associated with partial oc-cupation of non-jellium, 4d-type, levels located on the interior of the Pd 55 kernel. This shows that the superatom model can be used to rationalize the bonding and stability of spherical ligated group 10 clusters, despite their apparent 0electron count.[a] J.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Section: Resultsmentioning

confidence: 99%

“…Group 10 clusters of a certain size also tend to aggregate in a compact fashion. [28][29][30][31][32] However, no general electron-counting rules developed for high nuclearity spherical clusters [4] seem to apply to these species in a comprehensive manner. On one side, they often do not obey the classical Wade-Mingos rules.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Analysis of the Mackay Icosahedral Cluster Pd₅₅(PiPr₃)₁₂(μ₃‐CO)₂₀: An Open‐Shell 20‐Electron Superatom

Wei

Marchal

Astruc

et al. 2020

Chemistry A European J

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“…This opens the possibility to further employ 2 for the preparation of new clusters. [59,60] It is noteworthy that carbonyliron carbide and nitride clusters were recently found to be active for electrocatalysis. [61,62]…”

Section: Discussionmentioning

confidence: 99%

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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“…The oxoboryl complex trans-[(Cy 3 P) 2 BrPt(BO)] (2)r eacts with the Group 13 Lewis acids EBr 3 (E = Al, Ga, In) to form the 1:1 Lewis acid-base adducts trans-[(Cy 3 P) 2 BrPt(BOEBr 3 )] (6)(7)(8). This reactivity can be extended by using two equivalents of the re-spectiveL ewis acid EBr 3 (E = Al, Ga) to form the 2:1L ewis acidbase adducts trans-[(Cy 3 P) 2…”

Section: Resultsmentioning

confidence: 99%

“…Transition-metal complexes with carbon monoxide ligands constitute some of the oldest knowno rganometallic compounds [1] and are key intermediates in organic syntheses. [2][3][4][5][6][7] The immense importance of carbonyl complexes has spurred an interest in their isoelectronic and isolobal equivalents (Scheme 1). [8] Noteworthy in this regard are borylene ligands( D BR), which are isoelectronic and isolobal to CO ligands.…”

Section: Introductionmentioning

confidence: 99%

Platinum Oxoboryl Complexes as Substrates for the Formation of 1:1, 1:2, and 2:1 Lewis Acid–Base Adducts and 1,2‐Dipolar Additions

Bertsch

Brand

Braunschweig

et al. 2015

Chemistry A European J

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The oxoboryl complex trans-[(Cy3 P)2 BrPt(B≡O)] (2) reacts with the Group 13 Lewis acids EBr3 (E=Al, Ga, In) to form the 1:1 Lewis acid-base adducts trans-[(Cy3 P)2 BrPt(B≡OEBr3 )] (6-8). This reactivity can be extended by using two equivalents of the respective Lewis acid EBr3 (E=Al, Ga) to form the 2:1 Lewis acid-base adducts trans-[(Cy3 P)2 (Br3 Al-Br)Pt(B≡OAlBr3 )] (18) and trans-[(Cy3 P)2 (Br3 Ga-Br)Pt(B≡OGaBr3 )] (15). Another reactivity pattern was demonstrated by coordinating two oxoboryl complexes 2 to InBr3 , forming the 1:2 Lewis acid-base adduct trans-[{(Cy3 P)2 BrPt(B≡O)}2 InBr3 ] (20). It was also possible to functionalize the B≡O triple bond itself. Trimethylsilylisothiocyanate reacts with 2 in a 1,2-dipolar addition to form the boryl complex trans-[(Cy3 P)2 BrPt{B(NCS)(OSiMe3 )}] (27).

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Platinum Carbonyl Clusters Chemistry: Four Decades of Challenging Nanoscience

Cited by 70 publications

References 97 publications

Theoretical Analysis of the Mackay Icosahedral Cluster Pd₅₅(PiPr₃)₁₂(μ₃‐CO)₂₀: An Open‐Shell 20‐Electron Superatom

Theoretical Analysis of the Mackay Icosahedral Cluster Pd₅₅(PiPr₃)₁₂(μ₃‐CO)₂₀: An Open‐Shell 20‐Electron Superatom

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

Platinum Oxoboryl Complexes as Substrates for the Formation of 1:1, 1:2, and 2:1 Lewis Acid–Base Adducts and 1,2‐Dipolar Additions

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Platinum Carbonyl Clusters Chemistry: Four Decades of Challenging Nanoscience

Cited by 70 publications

References 97 publications

Theoretical Analysis of the Mackay Icosahedral Cluster Pd55(PiPr3)12(μ3‐CO)20: An Open‐Shell 20‐Electron Superatom

Theoretical Analysis of the Mackay Icosahedral Cluster Pd55(PiPr3)12(μ3‐CO)20: An Open‐Shell 20‐Electron Superatom

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

Platinum Oxoboryl Complexes as Substrates for the Formation of 1:1, 1:2, and 2:1 Lewis Acid–Base Adducts and 1,2‐Dipolar Additions

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Theoretical Analysis of the Mackay Icosahedral Cluster Pd₅₅(PiPr₃)₁₂(μ₃‐CO)₂₀: An Open‐Shell 20‐Electron Superatom

Theoretical Analysis of the Mackay Icosahedral Cluster Pd₅₅(PiPr₃)₁₂(μ₃‐CO)₂₀: An Open‐Shell 20‐Electron Superatom

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