Adducts of oxovanadium(IV) dithiocarbamates

1969 ◽  
Vol 47 (22) ◽  
pp. 4283-4286 ◽  
Author(s):  
B. Jack McCormick
Keyword(s):  
Dimethyl Sulfoxide ◽  
Molecular Orbital ◽  
Spectral Properties ◽  
Orbital Ordering ◽  
Mild Conditions ◽  
Spectral Evidence

Pyridine and 4-methylpyridine adducts of oxovanadium(IV) dithiocarbamates have been isolated and characterized as solids. It has been shown that the addenda can be removed under mild conditions with concomitant regeneration of the parent dithiocarbamate (DTC) complexes. Attempts to isolate dimethyl-sulfoxide adducts have not been successful, although spectral evidence suggests that adducts are formed in solution. A qualitative rationalization of the molecular orbital ordering and electronic spectral properties of the adducts is presented.

Radical Enzymes Control the Chemistry of Their Highly Reactive Intermediates Using the Quantum Coulombic Effect

2020 ◽  
Author(s):  
Hossein Khalilian ◽  
Gino A. DiLabio
Keyword(s):  
Hydrogen Bonding ◽  
Molecular Orbital ◽  
Reactive Intermediates ◽  
Hydrogen Bonding Interaction ◽  
Orbital Ordering ◽  
Dynamic Nature ◽  
Radical Intermediate ◽  
Highest Occupied Molecular Orbital ◽  
Bonding Interaction ◽  
Close Proximity

Here, we report an exquisite strategy that the B12 enzymes exploit to manipulate the reactivity of their radical intermediate (Adenosyl radical). Based on the quantum-mechanic calculations, these enzymes utilize a little known long-ranged through space quantum Coulombic effect (QCE). The QCE causes the radical to acquire an electronic structure that contradicts the Aufbau Principle: The singly-occupied molecular orbital (SOMO) is no longer the highest-occupied molecular orbital (HOMO) and the radical is unable to react with neighbouring substrates. The dynamic nature of the enzyme and its structure is expected to be such that the reactivity of the radical is not restored until it is moved into close proximity of the target substrate. We found that the hydrogen bonding interaction between the nearby conserved glutamate residue and the ribose ring of Adenosyl radical plays a crucial role in manipulating the orbital ordering

Radical Enzymes Control the Chemistry of Their Highly Reactive Intermediates Using the Quantum Coulombic Effect

2020 ◽  
Author(s):  
Hossein Khalilian ◽  
Gino A. DiLabio
Keyword(s):  
Hydrogen Bonding ◽  
Molecular Orbital ◽  
Reactive Intermediates ◽  
Hydrogen Bonding Interaction ◽  
Orbital Ordering ◽  
Dynamic Nature ◽  
Radical Intermediate ◽  
Highest Occupied Molecular Orbital ◽  
Bonding Interaction ◽  
Close Proximity

Here, we report an exquisite strategy that the B12 enzymes exploit to manipulate the reactivity of their radical intermediate (Adenosyl radical). Based on the quantum-mechanic calculations, these enzymes utilize a little known long-ranged through space quantum Coulombic effect (QCE). The QCE causes the radical to acquire an electronic structure that contradicts the Aufbau Principle: The singly-occupied molecular orbital (SOMO) is no longer the highest-occupied molecular orbital (HOMO) and the radical is unable to react with neighbouring substrates. The dynamic nature of the enzyme and its structure is expected to be such that the reactivity of the radical is not restored until it is moved into close proximity of the target substrate. We found that the hydrogen bonding interaction between the nearby conserved glutamate residue and the ribose ring of Adenosyl radical plays a crucial role in manipulating the orbital ordering

Molecular orbital ordering in titania and the associated semiconducting behavior

2011 ◽  
Vol 99 (14) ◽  
pp. 142104 ◽  
Author(s):  
Joseph Park ◽  
Kyung-Chul Ok ◽  
Byung Du Ahn ◽  
Je Hun Lee ◽  
Jae-Woo Park ◽  
...  
Keyword(s):  
Molecular Orbital ◽  
Orbital Ordering ◽  
Semiconducting Behavior

A Highly Efficient Method for the Bromination of Alkenes, Alkynes and Ketones Using Dimethyl Sulfoxide and Oxalyl Bromide

Synthesis ◽  
2018 ◽  
Vol 50 (21) ◽  
pp. 4325-4335 ◽  
Author(s):  
Hongyu Tian ◽  
Baoguo Sun ◽  
Rui Ding ◽  
Jiaqi Li ◽  
Wenyi Jiao ◽  
...  
Keyword(s):  
Dimethyl Sulfoxide ◽  
Efficient Method ◽  
Low Cost ◽  
Reaction Times ◽  
Attractive Alternative ◽  
Mild Conditions ◽  
Highly Efficient

The pairing of DMSO and oxalyl bromide is reported as a highly efficient brominating reagent for various alkenes, alkynes and ketones. This bromination approach demonstrates remarkable advantages, such as mild conditions, low cost, short reaction times, provides excellent yields in most cases and represents a very attractive alternative for the preparation of dibromides and α-bromoketones.

A Facile Approach to Catalyst-Free Cyanation and Azidation of ­Organic Compounds and a One-Pot Preparation of 5-Substituted 1H-Tetrazoles by Using a Dimethyl Sulfoxide–Nitric Acid Combination

Synlett ◽  
2019 ◽  
Vol 30 (20) ◽  
pp. 2290-2294
Author(s):  
Mohammad Ali Nasseri ◽  
Seyyedeh Ameneh Alavi ◽  
Boshra Mahmoudi ◽  
Milad Kazemnejadi
Keyword(s):  
Nitric Acid ◽  
Dimethyl Sulfoxide ◽  
Organic Compounds ◽  
Sodium Azide ◽  
Potassium Cyanide ◽  
Hydroxylamine Hydrochloride ◽  
One Pot ◽  
Mild Conditions ◽  
Tetrazole Derivatives

In this study, cyanations or azidations of imines were performed by using hydroxy(dimethyl)-λ4-sulfanecarbonitrile or azido(dimethyl)-λ4-sulfanol, respectively, prepared in situ by treatment of potassium cyanide or sodium azide with a dimethyl sulfoxide–nitric acid combination. Furthermore, a one-pot preparation of 5-substituted 1H-tetrazole derivatives was carried out by using this reagent combination in the presence of an aldehyde, hydroxylamine hydrochloride, and sodium azide under mild conditions.

Dna-Binding Compounds. IV. Synthesis and Solution Conformation of a Novel Macrocyle Formed by Coupling of the Side-Chains of Adjacent L-Lysine Residues

1991 ◽  
Vol 44 (11) ◽  
pp. 1649 ◽  
Author(s):  
AM Bray ◽  
DP Kelly ◽  
TK Lim
Keyword(s):  
Carboxylic Acid ◽  
Dimethyl Sulfoxide ◽  
The Novel ◽  
Two Dimensional ◽  
Amino Groups ◽  
Solution Conformation ◽  
Mild Conditions ◽  
Dimethyl Sulfoxide Solution ◽  
Acid Methyl ◽  
Lysine Residues

The novel macrocyclic dilysine derivatives (8S,11S)-11-t-butoxycarbonylamino-2,10-dioxo-1,3,9-triazacyclopentadecane-8-carboxylic acid methyl (5) and t-butyl (6) esters were prepared by coupling of the є-amino groups of adjacent lysine residues of the esters of Boc-Lys-Lys-OR with 1,1′-carbonyldiimidazole under mild conditions. The conformation of (6) in dimethyl sulfoxide solution was determined by the use of a variety of one- and two-dimensional n.m.r. techniques.

Unusual Molecular Orbital Ordering in Molybdenum−Ruthenium Heterometallic Porphyrin Dimers:  Structural and Magnetic Evidence

1998 ◽  
Vol 120 (31) ◽  
pp. 7999-8000 ◽  
Author(s):  
James P. Collman ◽  
Steven T. Harford ◽  
Pascale Maldivi ◽  
Jean-Claude Marchon
Keyword(s):  
Molecular Orbital ◽  
Orbital Ordering ◽  
Porphyrin Dimers

Theory of molecular orbital ordering and anomalous antiferromagnetism in V2O3

2002 ◽  
Vol 312-313 ◽  
pp. 696-697 ◽  
Author(s):  
R. Shiina ◽  
F. Mila ◽  
F.-C. Zhang ◽  
T.M. Rice
Keyword(s):  
Molecular Orbital ◽  
Orbital Ordering
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