Cross-conjugated pentadienyliron tricarbonyl cations. Dominance of frontier orbital interaction in metal-carbon bonding

1974 ◽  
Vol 96 (7) ◽  
pp. 2298-2300 ◽  
Author(s):  
Benedict R. Bonazza ◽  
C. Peter Lillya
Keyword(s):  
Orbital Interaction ◽  
Frontier Orbital ◽  
Carbon Bonding

A NEW ORBITAL INTERACTION ANALYSIS SYSTEM "LUMMOX" AND IT'S APPLICATION OF PHOSPHINE-PALLADIUM COMPLEXES

2005 ◽  
Vol 04 (01) ◽  
pp. 345-355 ◽  
Author(s):  
MASAHIRO YAMANAKA ◽  
AKINOBU SHIGA
Keyword(s):  
Interaction Analysis ◽  
Palladium Complexes ◽  
Orbital Interaction ◽  
Frontier Orbital ◽  
System A ◽  
Analysis System

A new orbital interaction analysis system, "LUMMOX", is based on two theories of "Paired Interacting Orbital (PIO)" and "Localized Frontier Orbital (LFO)", which have been developed by Fujimoto et al. LUMMOX can readily estimate the reactivity of an interacting system A–B of various sizes with the same A by comparing with the same number of the interacting orbitals. By applying LUMMOX, we report herein the primary orbital interaction on the phosphine-palladium complexes ( PF 3 Pd , PH 3 Pd , PMe 3 Pd , PPh 3 Pd ) continuously changes from the donative to back-donative interaction.

scholarly journals Tetrel Bond between 6-OTX3-Fulvene and NH3: Substituents and Aromaticity

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 10 ◽  
Author(s):  
Ming-Chang Hou ◽  
Shu-Bin Yang ◽  
Qing-Zhong Li ◽  
Jian-Bo Cheng ◽  
Hai-Bei Li ◽  
...  
Keyword(s):  
Interaction Energy ◽  
Electron Donor ◽  
Weak Interaction ◽  
Deformation Energy ◽  
Orbital Interaction ◽  
Interaction Type ◽  
Enhancing Effect ◽  
Tetrel Bond ◽  
Cyano Groups ◽  
Carbon Bonding

Carbon bonding is a weak interaction, particularly when a neutral molecule acts as an electron donor. Thus, there is an interesting question of how to enhance carbon bonding. In this paper, we found that the –OCH3 group at the exocyclic carbon of fulvene can form a moderate carbon bond with NH3 with an interaction energy of about −10 kJ/mol. The –OSiH3 group engages in a stronger tetrel bond than does the –OGeH3 group, while a reverse result is found for both –OSiF3 and –OGeF3 groups. The abnormal order in the former is mainly due to the stronger orbital interaction in the –OSiH3 complex, which has a larger deformation energy. The cyano groups adjoined to the fulvene ring not only cause a change in the interaction type, from vdW interactions in the unsubstituted system of –OCF3 to carbon bonding, but also greatly strengthen tetrel bonding. The formation of tetrel bonding has an enhancing effect on the aromaticity of the fulvene ring.

Theoretical studies of SN2 transition states. Substituent effects

1982 ◽  
Vol 60 (11) ◽  
pp. 1291-1294 ◽  
Author(s):  
Saul Wolfe ◽  
David John Mitchell ◽  
H. Bernhard Schlegel
Keyword(s):  
Gas Phase ◽  
Transition States ◽  
Substituent Effects ◽  
Orbital Interaction ◽  
Frontier Orbital ◽  
Orbital Interactions ◽  
Pyramidal Inversion ◽  
New Type ◽  
Constraint Effects ◽  
And Inversion

Similar substituent and angular constraint effects are noted for pyramidal inversion at tricoordinate nitrogen and inversion at a carbon centre undergoing an SN2 displacement reaction. The former process has been analyzed successfully by a quantitative PMO analysis which focuses on the frontier orbital interactions between X and NH2 in the planar and pyramidal structures of X—NH2 molecules having X = F, CH3, CHO. Based on total energy calculations at the 6-311G*//4-31G level, the effects of X upon the rates of the gas phase SN2 reactions F− + XCH2F → XCH2F + F− are found to be [Formula: see text]. Taking the treatment of nitrogen inversion as a precedent, the origin of this trend has been examined by a quantitative PMO analysis which focuses on the frontier orbital interactions between X and CH2F2− in the transition states, and between X and CH2F in the reactants. This has revealed that the rate enhancement associated with an α-carbonyl substituent in these SN2 reactions can be related to the presence of a stabilizing orbital interaction of a new type in the transition state, coupled to an exceptionally low destabilizing orbital interaction.

DOES P-YLIDIC RADICAL FEATURE THE YLIDIC OR RADICAL CHARACTER TOWARD FORMALDEHYDE?

2007 ◽  
Vol 06 (03) ◽  
pp. 531-540
Author(s):  
HONG-BIN XIE ◽  
YI-HONG DING
Keyword(s):  
Reaction Mechanism ◽  
Model Reaction ◽  
Orbital Interaction ◽  
Frontier Orbital ◽  
Orbital Theory ◽  
Title Reaction ◽  
Theoretical Investigations ◽  
Elimination Mechanism ◽  
Radical Character ◽  
Analogical Process

Theoretical investigations are preformed on the model reaction of PH 3 CH + H 2 CO to unravel reactivity of PH 3 CH , so-called Ylide-like radical, at G3MP2 and CCSD(T)/aug-cc-pVDZ//MP2/6-311++G(d,p) level. The results indicate that P -Ylidic radical behaves differently from the P -Ylide or usual unsaturated radical toward formaldehyde. For the entrance channels, [2+2] cycloaddition to form oxaphosphetane radical INT1 is more favorable, which is an analogical process to Witting reaction of P -Ylide. So PH 3 CH shows P -Ylide character in entrance channel, which has found the support from the dual one-center frontier–orbital interaction based on Fukui's frontier–orbital theory. However, due to the radical character of INT1, it can competitively give P2 PH 3 CHCHO + H and INT2, but not Witting-type products of alkene and phosphine oxide. At last, INT2 almost can barrierlessly fragmentate to Corey-type products of ethene oxide radical and phosphine. The present study shows that PH 3 CH , Ylide-like radical, has duplicate reactivity of both P-Ylide and radical, and title reaction presents a completely new reaction mechanism, compared with previous well-known H -abstract or addition–elimination mechanism for radical- H 2 CO reactions.

Dimer formation of NO ligands in the gas-phase halide ion clusters X−(NO) enhanced by a frontier orbital interaction

2000 ◽  
Vol 323 (1-2) ◽  
pp. 155-159 ◽  
Author(s):  
Kenzo Hiraoka ◽  
Tomoyuki Iino ◽  
Daisuke Eguchi ◽  
Takayuki Mizuno ◽  
Shinichi Yamabe
Keyword(s):  
Gas Phase ◽  
Orbital Interaction ◽  
Frontier Orbital ◽  
Dimer Formation ◽  
Ion Clusters

Nucleophilicity and its parametrization

1989 ◽  
Vol 54 (1) ◽  
pp. 117-135
Author(s):  
Oldřich Pytela ◽  
Vítězslav Zima
Keyword(s):  
Regression Analysis ◽  
Linear Correlation ◽  
Correlation Equation ◽  
Chemical Processes ◽  
General Tendency ◽  
Orbital Interaction ◽  
Physico Chemical ◽  
Physical And Chemical ◽  
Two Parameter ◽  
Better Than

The method of conjugate deviations based on the regression analysis has been suggested for construction of a new nucleophilicity scale. This method has been applied to a set of 28 nucleophiles participating in 47 physical and chemical processes described in literature. The two-parameter nucleophilicity scale obtained represents-in the parameter denoted as ND-the general tendency to form a bond to an electrophile predominantly on the basis of the orbital interaction and-in the parameter denoted as PD-the ability to interact with a centre similar to the proton (basicity). The linear correlation equation involving the ND, PD parameters and the charge appears to be distinctly better than the most significant relations used. The correlation dependences have the physico-chemical meaning. From the position of individual nucleophiles in the space of the ND and PD parameters, some general conclusions have been derived about the factors governing the reactivity of nucleophiles.

Niobocene Dichloride and Niobocene Diiodide: Electronic Absorption Spectra and Electron Spin Resonance

1998 ◽  
Vol 63 (5) ◽  
pp. 628-635 ◽  
Author(s):  
Jana Holubová ◽  
Zdeněk Černošek ◽  
Ivan Pavlík
Keyword(s):  
Absorption Spectra ◽  
Electronic Absorption ◽  
Electronic Absorption Spectra ◽  
Point Group ◽  
Esr Spectra ◽  
Ligand Field ◽  
Orbital Interaction ◽  
Symmetry Point Group ◽  
Spin Orbital ◽  
Halide Ligands

The effect of the halide ligand on the bonding of niobium in niobocene dichloride and niobocene diiodide was investigated. The electronic absorption spectra of the two compounds in the range of d-d transitions were resolved into four bands corresponding to transitions of the d1 electron between five frontier orbitals in a molecule of symmetry point group C2v. The energies of the frontier molecular orbitals were determined relatively to the energy of the orbitals in the spherically symmetric ligand field formed by the appropriate halide ligands. The effect of the halide ligands on the spin-orbital interaction of the HOMO orbital is discussed qualitatively on the basis the ESR spectra.

Catalysis with Supramolecular Carbon‐Bonding Interactions

2021 ◽  
Author(s):  
Wei Wang ◽  
Xinxin Li ◽  
Pan-Pan Zhou ◽  
Yao Wang
Keyword(s):  
Carbon Bonding

Catalysis with Supramolecular Carbon‐Bonding Interactions

2021 ◽  
Author(s):  
Wei Wang ◽  
Xinxin Li ◽  
Pan-Pan Zhou ◽  
Yao Wang
Keyword(s):  
Carbon Bonding
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