Coordination capabilities of anthracene ligand in binuclear sandwich complexes: DFT investigation

Bensalem, Narimene; Zouchoune, Bachir

doi:10.1007/s11224-016-0798-6

Cited by 18 publications

(3 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In order to explore and to understand the electronic structure, bonding properties, and chemical stability of the aforementioned binuclear complexes (Scheme 1), we provide a complete rationalization of their bonding by means of a theoretical DFT analysis using the generalized gradient approximation (BP86) and the hybrid B3LYP* levels and supported by the energy decomposition analysis (EDA) [50–52] exploiting the σ‐donation (L → M) and π‐backdonation (L ← M) capabilities of the interacting ligands [53, 54]. These functionals have been proved to reproduce the available experimental data and investigate the electronic properties of related mono‐ and dinuclear transition metal complexes [29, 55–69].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

“…M) and π-backdonation (L M) capabilities of the interacting ligands [53,54]. These functionals have been proved to reproduce the available experimental data and investigate the electronic properties of related mono-and dinuclear transition metal complexes [29,[55][56][57][58][59][60][61][62][63][64][65][66][67][68][69].…”

mentioning

confidence: 99%

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

Self Cite

View full text Add to dashboard Cite

show abstract

“…Compound 8 is also of interest as a reduced version of the hypothetical neutral monomeric V 2 An 2 , a possible precursor to the unknown oligomeric [V 2 An] 1 , which has been proposed to be of possible utility as a 'vanadium-anthracene wire' (Wang et al, 2008). A DFT (density functional theory) computational investigation of presently unknown M 2 An 2 complexes (M = Ti-Ni) is also of interest (Bensalem & Zouchoune, 2016).…”

Section: Introductionmentioning

confidence: 99%

Syntheses and crystal structures of new naphthalene– and anthracene–vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran)₃][V₂(anthracene)₂]

2022

View full text Add to dashboard Cite

Reduction of bis(naphthalene)vanadium(0) by potassium naphthalene (KNp) in tetrahydrofuran (THF) provides a highly reactive, thermolabile, and so far unisolable brown substance, which affords the first reported derivatives of bis(naphthalene)vanadates. From these solutions, thermally stable (298 K) and structurally characterized compounds have been obtained, including dark-red rods of catena-poly[bis(μ3-η4:η6:η4-naphthalene)tetrakis(tetrahydrofuran)dipotassiumvanadium], [K2V(C4H8O)4(C10H8)2] n or [K(THF)2]2[V(C10H8)2] (3), and red plates of (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)potassium [1,2-bis(dimethylphosphanyl)ethane]bis(η4-naphthalene)vanadium tetrahydrofuran monosolvate, [K(C18H36N2O6)][V(C10H8)2(C6H16P2)]·C4H8O or [K([2.2.2]cryptand)][V(C10H8)2(dmpe)]·THF [dmpe is 1,2-bis(dimethylphosphanyl)ethane] (4b). Notably, [V(C10H8)2]2− is the only example of a structurally authenticated homoleptic bis(arene)metallate dianion and was obtained by further reduction of the brown material by KNp in THF, in the presence of trimethylphosphane (PMe3). Addition of anthracene (An) to the brown material in THF afforded deep-violet and paramagnetic crystalline (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium [(η4-anthracene)(tetrahydrofuran)vanadium]-μ-η4:η2-anthracene-[(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium]-μ-η2:η4-anthracene-[(η4-anthracene)(tetrahydrofuran)vanadium] tetrahydrofuran disolvate, [K(C12H24O6)(C4H8O)2][KV2(C12H24O6)(C4H8O)2(C14H10)4]·2C4H8O or [K(18-crown-6)][K(18-crown-6)(THF)2][V(C14H10)2(THF)]2·2(THF) (5), which readily reacted with PMe3 and dmpe to give new vanadate salts. These were structurally characterized as (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium bis(η4-anthracene)(trimethylphosphane)vanadium tetrahydrofuran monosolvate, [K(C12H24O6)(C4H8O)2][V(C14H10)2(C3H9P)]·C4H8O or [K(18-crown-6)(THF)2][V(C14H10)2(PMe3)]·THF (6), and tetrakis(1,2-dimethoxyethane)potassium bis(η4-anthracene)[1,2-bis(dimethylphosphanyl)ethane]vanadium, [K(C4H10O2)4][V(C14H10)2(C6H16P2)] or [K(DME)4][V(C14H10)2(dmpe)] (DME is 1,2-dimethoxyethane) (7b). The last three structures contain the first known bis(anthracene)vanadates and are thereby derivatives of the unknown bis(anthracene)vanadium(0). Attempts to obtain the sodium salt analog of 5 in THF resulted instead in the formation of a unique substance, (μ3-η6:η6:η6-anthracene)(μ2-η6:η6-anthracene)tris(tetrahydrofuran)sodiumdivanadium, [NaV2(C14H10)2(C4H8O)3] or [Na(THF)3][V2(C14H10)2] (8), containing the first reported dimetallabis(anthracene) sandwich compound.

show abstract

Electronic structure and structural diversity in indenyl in heterobinuclear transition-metal half-sandwich complexes

et al. 2018

View full text Add to dashboard Cite

Coordination capabilities of anthracene ligand in binuclear sandwich complexes: DFT investigation

Cited by 18 publications

References 50 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)

Syntheses and crystal structures of new naphthalene– and anthracene–vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran)₃][V₂(anthracene)₂]

Electronic structure and structural diversity in indenyl in heterobinuclear transition-metal half-sandwich complexes

Contact Info

Product

Resources

About

Coordination capabilities of anthracene ligand in binuclear sandwich complexes: DFT investigation

Cited by 18 publications

References 50 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)

Syntheses and crystal structures of new naphthalene– and anthracene–vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran)3][V2(anthracene)2]

Electronic structure and structural diversity in indenyl in heterobinuclear transition-metal half-sandwich complexes

Contact Info

Product

Resources

About

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)

Syntheses and crystal structures of new naphthalene– and anthracene–vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran)₃][V₂(anthracene)₂]