Lone-Pair Activity in Lead(II) Complexes with Unsymmetrical Lariat Ethers

2006 ◽  
Vol 45 (14) ◽  
pp. 5407-5416 ◽  
Author(s):  
David Esteban-Gómez ◽  
Carlos Platas-Iglesias ◽  
Teresa Enríquez-Pérez ◽  
Fernando Avecilla ◽  
Andrés de Blas ◽  
...  
Keyword(s):  
2020 ◽  
Author(s):  
Olivier Charles Gagné

The scarcity of nitrogen in Earth’s crust, combined with challenging synthesis, have made inorganic nitrides a relatively-unexplored class of compounds compared to their naturally-abundant oxide counterparts. To facilitate exploration of their compositional space via <i>a priori</i> modeling, and to help <i>a posteriori</i> structure verification not limited to inferring the oxidation state of redox-active cations, we derive a suite of bond-valence parameters and Lewis-acid strength values for 76 cations observed bonding to N<sup>3-</sup>, and further outline a baseline statistical knowledge of bond lengths for these compounds. We examine structural and electronic effects responsible for the functional properties and anomalous bonding behavior of inorganic nitrides, and identify promising venues for exploring uncharted compositional spaces beyond the reach of high-throughput computational methods. We find that many mechanisms of bond-length variation ubiquitous to oxide and oxysalt compounds (e.g., lone-pair stereoactivity, the Jahn-Teller and pseudo Jahn-Teller effects) are similarly pervasive in inorganic nitrides, and are occasionally observed to result in greater distortion magnitude than their oxide counterparts. We identify inorganic nitrides with multiply-bonded metal ions as a promising venue in heterogeneous catalysis, e.g. in the development of a post-Haber-Bosch process proceeding at milder reaction conditions, thus representing further opportunity in the thriving exploration of the functional properties of this emerging class of materials.<br>


2017 ◽  
Author(s):  
Arpita Yadav ◽  
Dasari L V K Prasad ◽  
Veejendra Yadav

<p>The torquoselectivity, the inward or outward ring opening of 3-substituted cyclobutenes, is conventionally guided by the donor and/or acceptor ability of the substituent (S). It is typically predicted by estimating the respective ring opening transition state (TS) barriers. While there is no known dissent in regard to the outward rotation of electron-rich substituents from the approaches of TS calculations, the inward rotation was predicted for some electron-accepting substituents and outward for others. To address this divergence in predicting the torquoselectivity, we have used reliable orbital descriptors through natural bond orbital theoretical calculations and demonstrated that (a) interactions <i>n</i><i><sub>S</sub></i>→s*<sub>C3C4</sub> for a lone pair containing substituent, s<sub>S</sub>→s*<sub>C3C4</sub> for a s-donor substituent, s<sub>C3C4</sub>→p*<sub>S</sub> for a resonance-accepting substituent and s<sub>C3C4</sub>→s*<sub>S</sub> for a s-acceptor substituent constitute the true electronic controls of torquoselectivity, and (b) reversibility of the ring opening event is an additional important contributor to the observed product distribution.</p>


Author(s):  
Olivier Charles Gagné ◽  
Frank Christopher Hawthorne

Bond-length distributions are examined for thirty-three configurations of the metalloid ions and fifty-six configurations of the post-transition-metal ions bonded to oxygen. Lone-pair stereoactivity is discussed.


Author(s):  
Olivier Charles Gagné ◽  
Frank Christopher Hawthorne

Bond-length distributions are examined for thirty-three configurations of the metalloid ions and fifty-six configurations of the post-transition-metal ions bonded to oxygen. Lone-pair stereoactivity is discussed.


Author(s):  
Olivier Charles Gagné ◽  
Frank Christopher Hawthorne

Bond-length distributions are examined for three configurations of the H+ ion, sixteen configurations of the group 14-16 non-metal ions and seven configurations of the group 17 ions bonded to oxygen. Lone-pair stereoactivity for ions bonded to O<sup>2-</sup> is discussed, as well as the polymerization of the PO<sub>4</sub> group.


2021 ◽  
Author(s):  
Anna A Mukhacheva ◽  
Tatyana Asanova ◽  
Maxim R. Ryzikov ◽  
Taisiya Sergeevna Sukhikh ◽  
Nikolay B. Kompankov ◽  
...  
Keyword(s):  

Bi3+ and Pb2+ uptake by [PW11O39]7– monolacunary Keggin-type anion leads to the formation of [PW11O39Bi]4– and [PW11O39Pb]5– complexes with stereochemically active lone pair at the incorporated heterometal. Both complexes were...


2021 ◽  
Vol 23 (15) ◽  
pp. 9121-9129
Author(s):  
Weixing Li ◽  
Imanol Usabiaga ◽  
Camilla Calabrese ◽  
Luca Evangelisti ◽  
Assimo Maris ◽  
...  
Keyword(s):  

Stronger and more flexible lone pair⋯π–hole interaction of ammonia with respect to water in complexes with perfluorinated arenes.


RSC Advances ◽  
2020 ◽  
Vol 10 (66) ◽  
pp. 40391-40394
Author(s):  
Willy Carrasquel-Ursulaez ◽  
Ryan D. Reeves ◽  
Mahzad Dehghany ◽  
Corey Jones ◽  
Jennifer M. Schomaker ◽  
...  
Keyword(s):  

The cytotoxicity of dialkylated lariat ethers has been previously attributed to their ionophoric properties.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Samuel Tetteh ◽  
Albert Ofori

Abstract The M–Ccarbene bond in metal (M) complexes involving the imidazol-2-ylidene (Im) ligand has largely been described using the σ-donor only model with donation of σ electrons from the sp-hybridized orbital of the carbene carbon into vacant orbitals on the metal centre. Analyses of the M–Ccarbene bond in a series of group IA, IIA and IIIA main group metal complexes show that the M-Im interactions are mostly electrostatic with the M–Ccarbene bond distances greater than the sum of the respective covalent radii. Estimation of the binding energies of a series of metal hydride/fluoride/chloride imidazol-2-ylidene complexes revealed that the stability of the M–Ccarbene bond in these complexes is not always commensurate with the σ-only electrostatic model. Further natural bond orbital (NBO) analyses at the DFT/B3LYP level of theory revealed substantial covalency in the M–Ccarbene bond with minor delocalization of electron density from the lone pair electrons on the halide ligands into antibonding molecular orbitals on the Im ligand. Calculation of the thermodynamic stability of the M–Ccarbene bond showed that these interactions are mostly endothermic in the gas phase with reduced entropies giving an overall ΔG > 0.


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