Counterintuitive consequences of filled ligand .pi. interactions with metal d orbitals

1980 ◽  
Vol 19 (12) ◽  
pp. 3865-3866 ◽  
Author(s):  
John L. Hubbard ◽  
Dennis L. Lichtenberger
Keyword(s):  
Pi Interactions ◽  
D Orbitals

Mechanically-Tunable Quantum Interference in Ferrocene-Based Single-Molecule Junctions

2020 ◽  
Author(s):  
María Camarasa-Gómez ◽  
Daniel Hernangómez-Pérez ◽  
Michael S. Inkpen ◽  
Giacomo Lovat ◽  
E-Dean Fung ◽  
...  
Keyword(s):  
Single Molecule ◽  
Quantum Interference ◽  
Degrees Of Freedom ◽  
Building Blocks ◽  
Ferrocene Derivative ◽  
Single Molecule Junctions ◽  
Molecule Junction ◽  
Single Molecule Junction ◽  
The Impact ◽  
D Orbitals

Ferrocenes are ubiquitous organometallic building blocks that comprise a Fe atom sandwiched between two cyclopentadienyl (Cp) rings that rotate freely at room temperature. Of widespread interest in fundamental studies and real-world applications, they have also attracted<br>some interest as functional elements of molecular-scale devices. Here we investigate the impact of<br>the configurational degrees of freedom of a ferrocene derivative on its single-molecule junction<br>conductance. Measurements indicate that the conductance of the ferrocene derivative, which is<br>suppressed by two orders of magnitude as compared to a fully conjugated analog, can be modulated<br>by altering the junction configuration. Ab initio transport calculations show that the low conductance is a consequence of destructive quantum interference effects that arise from the hybridization of metal-based d-orbitals and the ligand-based π-system. By rotating the Cp rings, the hybridization, and thus the quantum interference, can be mechanically controlled, resulting in a conductance modulation that is seen experimentally.<br>

Stereospecific 1,3-H Transfer of Indenols Proceeds via Persistent Ion-Pairs Anchored By NH···Pi Interactions

2018 ◽  
Author(s):  
David Ascough ◽  
Fernanda Duarte ◽  
Robert Paton
Keyword(s):  
Computational Analysis ◽  
Ion Pairs ◽  
Ion Pair ◽  
Hydrogen Atom Transfer ◽  
Polar Solvents ◽  
Chirality Transfer ◽  
Activation Barriers ◽  
Sense And Avoid ◽  
Phase Dynamics ◽  
Pi Interactions

The base-catalyzed rearrangement of arylindenols is a rare example of a suprafacial [1,3]-hydrogen atom transfer. The mechanism has been proposed to proceed via sequential [1,5]-sigmatropic shifts, which occur in a selective sense and avoid an achiral intermediate. A computational analysis using quantum chemistry casts serious doubt on these suggestions: these pathways have enormous activation barriers and in constrast to what is observed experimentally, they overwhelmingly favor a racemic product. Instead we propose that a suprafacial [1,3]-prototopic shift occurs in a two-step deprotonation/reprotonation sequence. This mechanism is favored by 15 kcal mol<sup>-1</sup> over that previously proposed. Most importantly, this is also consistent with stereospecificity since reprotonation occurs rapidly on the same p-face. We have used explicitly-solvated molecular dynamics studies to study the persistence and condensed-phase dynamics of the intermediate ion-pair formed in this reaction. Chirality transfer is the result of a particularly resilient contact ion-pair, held together by electrostatic attraction and a critical NH···p interaction which ensures that this species has an appreciable lifetime even in polar solvents such as DMSO and MeOH.

Regulating the electron filling state of d orbitals in Ta-based compounds for tunable lithium‑sulfur chemistry

2021 ◽  
pp. e00271
Author(s):  
Da Sun ◽  
Jianbin Zhou ◽  
Dewei Rao ◽  
Linqin Zhu ◽  
Shuwen Niu ◽  
...  
Keyword(s):  
Sulfur Chemistry ◽  
D Orbitals ◽  
Filling State ◽  
Lithium Sulfur

ChemInform Abstract: THE ROLE OF D ORBITALS ON PHOSPHORUS IN THE BONDING OF TRIMETHYLPHOSPHINE AND TRIS(TRIFLUOROMETHYL)PHOSPHINE

1982 ◽  
Vol 13 (33) ◽  
Author(s):  
M.-H. WHANGBO ◽  
K. R. STEWART
Keyword(s):  
D Orbitals

Unusually Strong Interactions Mediated by Both .pi.-.pi. Stacking and CH-.pi. Interactions Present in the Dimer of Nickel(II) Complex Coordinated with n-Butyl-Substituted Salen

1995 ◽  
Vol 117 (8) ◽  
pp. 2377-2378 ◽  
Author(s):  
Kazuo Miyamura ◽  
Akiko Mihara ◽  
Takashi Fujii ◽  
Yohici Gohshi ◽  
Youichi Ishii
Keyword(s):  
Strong Interactions ◽  
Pi Stacking ◽  
Pi Interactions

The role of sulfur d-orbitals in the charge-transfer complexation of carbonyl cyanide with alkyl sulfides

Tetrahedron ◽  
1976 ◽  
Vol 32 (12) ◽  
pp. 1345-1346 ◽  
Author(s):  
T. Fueno ◽  
Y. Yonezawa
Keyword(s):  
Charge Transfer ◽  
Carbonyl Cyanide ◽  
Charge Transfer Complexation ◽  
D Orbitals

The nature of .pi.-.pi. interactions

1990 ◽  
Vol 112 (14) ◽  
pp. 5525-5534 ◽  
Author(s):  
Christopher A. Hunter ◽  
Jeremy K. M. Sanders
Keyword(s):  
Pi Interactions

scholarly journals Crystalline splitting of d orbitals in two-dimensional regular optical lattices

2018 ◽  
Vol 98 (5) ◽  
Author(s):  
Hua Chen ◽  
X. C. Xie
Keyword(s):  
Optical Lattices ◽  
Two Dimensional ◽  
D Orbitals
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