Nature of the metal–ligand bond in some [(CO)4M ← BIIM(R)] {M = Cr, Mo, W; R = H, F, Cl, Br} complexes: A theoretical study

Bayat, Mehdi; Hatami, Masoud

doi:10.1016/j.poly.2016.02.022

Cited by 27 publications

(9 citation statements)

References 28 publications

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“…It has been shown that BP86 is a suitable level for the calculation of the bonding situation between the M ← L in complexes such as these [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50]. Vibrational frequency analyses, done at the same level of theory, indicated that the optimized structures are at the stationary points corresponding to the local minima without any imaginary frequency.…”

Section: Computational Details (Theoretical Studies)mentioning

confidence: 99%

New complexes of Ni(II) and Cu(II) with tridentate ONO Schiff base ligand: synthesis, crystal structures, electrochemical and theoretical investigation

et al. 2018

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In this research, we prepared a new series of the Cu(II) (1) and Ni(II) (2) metal complexes of a tridentate Schiff base ligand, (E)-2-(5-bromo-2-hydroxybenzylideneamino) phenol (H 2 L). These complexes were characterized by elemental analysis, FT-IR, UV-Vis, and 1 H-NMR spectroscopy. The crystal structures of (1) and (2) were determined by X-ray diffraction studies. The single crystal X-ray diffraction analyses revealed that copper(II) cation is five-coordinated and the coordination polyhedron is a slightly distorted square pyramid. Nickel(II), on the other hand, is four-coordinated, and has a regular, square planar geometry. Further discussed were the electrochemical reduction of these complexes. We also analyzed the nature of the metal-ligand bond in the complexes through NBO and EDA analysis. Besides, vibrational sample magnetometer (VSM) revealed complex (1) was ferromagnetic.

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Section: Computational Details (Theoretical Studies)mentioning

confidence: 99%

New complexes of Ni(II) and Cu(II) with tridentate ONO Schiff base ligand: synthesis, crystal structures, electrochemical and theoretical investigation

et al. 2018

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“…the ETS-NOCV approach has emerged as a very precious tool for shedding light on the nature of metal-to-ligand interactions, as documented in the different cases studied. [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] In the present study, we applied ETS-NOCV to a series of [Mo(CO) 4 -(phen*)] complexes (phen* = substituted 1,10-phenanthroline) with the purpose of describing and quantifying the σ-donor and π-acceptor properties of phen* depending on their substitution. Among others, 1,10-phenanthrolines form a ubiquitous, significant class of ligands [32] that find application as fluorescent receptors, [33] antennae in luminescent metal complexes, [34] and in the synthesis of highly emitting phosphorescent compounds, [35] to name but a few.…”

Section: Introductionmentioning

confidence: 99%

A Quantitative Description of the σ‐Donor and π‐Acceptor Properties of Substituted Phenanthrolines

et al. 2016

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The bond between molybdenum and substituted 1,10-phenanthroline ligands in a series of [Mo(CO)4(phen*)]\ud complexes has been studied by combining experimental data (νCO) with DFT calculations. First, natural orbitals for chemical valence (NOCV) were calculated: The resulting charge-transfer magnitudes (Δqi) associated with the deformation density channels (Δρi) were related to σ-donation and π-back-donation.\ud Then, energy decomposition analysis was performed by applying the extended transition state (ETS) scheme. The outcomes of the ETS-NOCV approach has allowed us to quantify the energetic contribution of both ligand-to-metal (Eσ) and metal-to ligand (Eπ) interactions. A new parameter (Tphen) has been introduced comprising both Eσ and Eπ and thus providing a descriptor for the overall electronic contribution given by phenanthrolines\ud to the metal–ligand bond. This was corroborated by the linear correlation found between Tphen and the νCO vibration\ud modes of [Mo(CO)4(phen*)] complexes, at least for those containing a 2,9-unsubstituted phenanthroline. The case of\ud [Mo(CO)4(phen*)] derivatives with a 2,9-substituted phen* is also discussed

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“…Morokuma and Ziegler and Rauk developed EDA in the 1970s. Using this technique, a quantitative computational pattern is in hand for the explanation of the strength of M ← L σ donation, and M → L back‐bonding in main group and transition metal complexes with different types of ligands …”

Section: Resultsmentioning

confidence: 99%

“…All calculations were performed using the Gaussian 09 set of programs . It has been shown in former studies that BP86 is a suitable level for calculation of the bonding situation of M ← L in such as these complexes . For bonding analyses, the terms of EDA were carried out at BP86/TZ2P(ZORA)//BP86/def2‐SVP with C1 symmetry.…”

Section: Methodsmentioning

confidence: 99%

“…[36] It has been shown in former studies that BP86 is a suitable level for calculation of the bonding situation of M ← L in such as these complexes. [37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52] For bonding analyses, the terms of EDA were carried out at BP86/TZ2P(ZORA)//BP86/def2-SVP with C1 symmetry. The basis sets for all elements have triple-ζ quality augmented by one set of polarization functions (ADF basis set TZ2P (ZORA)) with the program package ADF2009.01.…”

Section: Computational Studiesmentioning

confidence: 99%

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Spectral, crystallographic, theoretical and antibacterial studies of palladium(II)/platinum(II) complexes with unsymmetric diphosphine ylides

Sabounchei

Badpa

Bayat

et al. 2018

Applied Organom Chemis

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The reaction of α‐keto‐stabilized diphosphine ylides [Ph2P(CH2)nPPh2═C(H)C(O)C6H4‐p‐CN] (n = 1 (Y1); n = 2 (Y2)) with dibromo(1,5‐cyclooctadiene) palladium(II)/platinum(II) complexes, [Pd/PtBr2(cod)], in equimolar ratio gave the new cyclometalated Pd(II) and Pt(II) complexes [Br2Pd(κ2‐Y1)] (1), [Br2Pt(κ2‐Y1)] (2), [Br2Pd(κ2‐Y2)] (3) and [Br2Pt(κ2‐Y2)] (4). These compounds were screened in a search for novel antibacterial agents and characterized successfully using Fourier transfer infrared and NMR (1H, 13C and 31P) spectroscopic methods. Also, the structures of complexes 1 and 2 were characterized using X‐ray crystallography. The results showed that the P,C‐chelated complexes 1 and 2 have structures consisting of five‐membered rings, while 3 and 4 have six‐membered rings, formed by coordination of the ligand through the phosphine group and the ylidic carbon atom to the metal centre. Also, a theoretical study of the structures of complexes 1–4 was conducted at the BP86/def2‐SVP level of theory. The nature of metal–ligand bonds in the complexes was investigated using energy decomposition analyses (EDA) and extended transition state combined with natural orbitals for chemical valence analyses. The results of EDA confirmed that the main portions of ΔEint, about 57–58%, in the complexes are allocated to ΔEelstat.

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Nature of the metal–ligand bond in some [(CO)4M ← BIIM(R)] {M = Cr, Mo, W; R = H, F, Cl, Br} complexes: A theoretical study

Cited by 27 publications

References 28 publications

New complexes of Ni(II) and Cu(II) with tridentate ONO Schiff base ligand: synthesis, crystal structures, electrochemical and theoretical investigation

New complexes of Ni(II) and Cu(II) with tridentate ONO Schiff base ligand: synthesis, crystal structures, electrochemical and theoretical investigation

A Quantitative Description of the σ‐Donor and π‐Acceptor Properties of Substituted Phenanthrolines

Spectral, crystallographic, theoretical and antibacterial studies of palladium(II)/platinum(II) complexes with unsymmetric diphosphine ylides

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