Coordination and ligands’ effects in trinuclear [Pd3(COT)2(L)]2+ (L = H2O, CO, N2, HCN, HNC, NH3, PH3, PCl3, PF3, CS, CH2) sandwich complexes of cyclooctatetraene: theoretical investigation

Benmachiche, Akila; Zouchoune, Bachir

doi:10.1007/s11224-019-01351-8

Cited by 6 publications

(2 citation statements)

References 56 publications

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“…The outstanding discrepancy comes from the contributions into the total interaction energy. Indeed, the ΔE elstat (≈50%) and ΔE orb (≈50%) contributions into the total attraction energy (ΔE elstat + ΔE orb ) are comparable in the carbonyls case, but in the of triethylphosphines, the ΔE orb falls to 35% in favor of the electrostatic one attaining 65% as obtained in previous works [47,[107][108][109][110]. Thus, an ionic character is dominant in PEt 3 complexes against equilibrium between ionic and covalent characters in carbonyl species.…”

Section: Bonding Analysissupporting

confidence: 74%

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)

Mecheri

Zouchoune

2023

Int J of Quantum Chemistry

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A theoretical DFT investigation has been achieved on (X)[M2Cl]L2 (M = Cr, Fe, L = CO, PEt3, and X = allyl, cyclopentadienyl, and indenyl) complexes by means of BP86 and B3LYP* functionals. The geometry optimizations showed an η3‐coordination for the allyl, while Cp and indenyl ligands adopt the same η5‐coordination mode and the chloride acts as bridging ligand. The metal–metal bond distances are very sensitive to the replacement of the CO with PEt3 (triethylphosphine) with regard to the electron‐donation and electron π‐backdonation properties for the former and only to the electron‐donation for the later. This replacement impacts drastically the metal–metal bonding. Changing the metal from Cr to Fe increases the metal–metal bond distance, decreases the bond order and the oxidation sate of Fe, in agreement with the decrease of Wiberg bond indices (WBI) and Mayer bond order values (MBO). The findings showed that the Cl− and allyl− behave as 4‐electron donors, while Cp− and Ind− behave as 6–electron donors leading to outstanding electron properties stemming from different coordination, which are clarified by the σ‐donation and π‐backdonation properties, which are highlighted by the orbitals' populations and the energy decomposition analysis (EDA). Based on the aforementioned information, the chromium and iron complexes of Cl− and allyl− are of 22‐ and 24‐metal valence electrons (MVE), where those of Cp− and Ind− are of 26‐ and 28‐MVE, respectively. It is well noted that the metal–metal multiple bonding overcomes the electrons' deficiency.

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Section: Bonding Analysissupporting

confidence: 74%

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)

Mecheri

Zouchoune

2023

Int J of Quantum Chemistry

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“…Trinuclear mixed-metal sandwich complexes could also construct axially chiral metal skeletons by selective dimerization [ 180 ]. The coordination modes and ligand influences for cyclooctatetraene ligated trinuclear Pd3 sandwich complexes were theoretically investigated [ 181 ]. Trinuclear Pd metal sheet sandwich complexes have peculiar electronic structures and hold great potential for further functionalization [ 182 ].…”

Section: Experimental and Theoretical Developments Of Triangular All-...mentioning

confidence: 99%

Advances for Triangular and Sandwich-Shaped All-Metal Aromatics

Wang,

Wang

2024

Molecules

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Much experimental work has been contributed to all-metal σ, π and δ-aromaticity among transition metals, semimetallics and other metals in the past two decades. Before our focused investigations on the properties of triangular and sandwich-shaped all-metal aromatics, A. I. Boldyrev presented general discussions on the concepts of all-metal σ-aromaticity and σ-antiaromaticity for metallo-clusters. Schleyer illustrated that Nucleus-Independent Chemical Shifts (NICS) were among the most authoritative criteria for aromaticity. Ugalde discussed the earlier developments of all-metal aromatic compounds with all possible shapes. Besides the theoretical predictions, many stable all-metal aromatic trinuclear clusters have been isolated as the metallic analogues of either the σ-aromatic molecule’s [H3]+ ion or the π-aromatic molecule’s [C3H3]+ ion. Different from Hoffman’s opinion on all-metal aromaticity, triangular all-metal aromatics were found to hold great potential in applications in coordination chemistry, catalysis, and material science. Triangular all-metal aromatics, which were theoretically proved to conform to the Hückel (4n + 2) rule and possess the smallest aromatic ring, could also play roles as stable ligands during the formation of all-metal sandwiches. The triangular and sandwich-shaped all-metal aromatics have not yet been specifically summarized despite their diversity of existence, puissant developments and various interesting applications. These findings are different from the public opinion that all-metal aromatics would be limited to further applications due to their overstated difficulties in synthesis and uncertain stabilities. Our review will specifically focus on the summarization of theoretical predictions, feasible syntheses and isolations, and multiple applications of triangular and sandwich shaped all-metal aromatics. The appropriateness and necessities of this review will emphasize and disseminate their importance and applications forcefully and in a timely manner.

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Bonding and electronic structures in dinuclear (X)[(Ind)M2L2] complexes (M = Ni, Pd, L = CO, PEt3, X = Cl, Allyl, Ind = indenyl, Cp = cyclopentadienyl): analogy between four-electron donor ligands

2019

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Coordination and ligands’ effects in trinuclear [Pd3(COT)2(L)]2+ (L = H2O, CO, N2, HCN, HNC, NH3, PH3, PCl3, PF3, CS, CH2) sandwich complexes of cyclooctatetraene: theoretical investigation

Cited by 6 publications

References 56 publications

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)

Advances for Triangular and Sandwich-Shaped All-Metal Aromatics

Bonding and electronic structures in dinuclear (X)[(Ind)M2L2] complexes (M = Ni, Pd, L = CO, PEt3, X = Cl, Allyl, Ind = indenyl, Cp = cyclopentadienyl): analogy between four-electron donor ligands

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Coordination and ligands’ effects in trinuclear [Pd3(COT)2(L)]2+ (L = H2O, CO, N2, HCN, HNC, NH3, PH3, PCl3, PF3, CS, CH2) sandwich complexes of cyclooctatetraene: theoretical investigation

Cited by 6 publications

References 56 publications

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M2Cl]L2complexes (M = Cr,Fe,L = CO,PEt3,X = Cl, allyl,Cp, and indenyl)

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M2Cl]L2complexes (M = Cr,Fe,L = CO,PEt3,X = Cl, allyl,Cp, and indenyl)

Advances for Triangular and Sandwich-Shaped All-Metal Aromatics

Bonding and electronic structures in dinuclear (X)[(Ind)M2L2] complexes (M = Ni, Pd, L = CO, PEt3, X = Cl, Allyl, Ind = indenyl, Cp = cyclopentadienyl): analogy between four-electron donor ligands

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Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M₂Cl]L₂complexes (M = Cr,Fe,L = CO,PEt₃,X = Cl, allyl,Cp, and indenyl)