Steric and inductive effects on the basicity of porphyrins and on the site of protonation of porphyrin dianions: radiolytic reduction of porphyrins and metalloporphyrins to chlorins or phlorins

1993 ◽  
Vol 89 (3) ◽  
pp. 495 ◽  
Author(s):  
Timothy P. G. Sutter ◽  
Rahmatollah Rahimi ◽  
Peter Hambright ◽  
Jerry C. Bommer ◽  
Manmohan Kumar ◽  
...  
Keyword(s):  
Inductive Effects ◽  
Radiolytic Reduction ◽  
Porphyrin Dianions

ChemInform Abstract: STRUCTURE OF FLUOROMETHYL RADICALS. CONJUGATIVE AND INDUCTIVE EFFECTS

1978 ◽  
Vol 9 (25) ◽  
Author(s):  
F. BERNARDI ◽  
W. CHERRY ◽  
S. SHAIK ◽  
N. D. EPIOTIS
Keyword(s):  
Inductive Effects ◽  
Abstract Structure

The addition of 2,4-dinitrobenzenesulphenyl chloride to 1,3-disubstituted allenes: a reexamination

1979 ◽  
Vol 57 (1) ◽  
pp. 119-127 ◽  
Author(s):  
Dennis G. Garratt ◽  
Pierre Beaulieu
Keyword(s):  
Double Bond ◽  
Chloride Solution ◽  
Methylene Chloride ◽  
Effective Mechanism ◽  
Substituent Group ◽  
Methylene Chloride Solution ◽  
Inductive Effects ◽  
Allene System

The reaction of 2,4-dinitrobenzenesulphenyl chloride with eight alkyl 1,3-disubstituted allenes in methylene chloride solution has been investigated. In contrast to earlier reports, attack by sulphur is found to occur exclusively at the central allenic carbon. The direction of approach of sulphenyl chloride leads preferentially to the formation of the E isomers in accord with the concept of steric approach control. The ratio of E to Z alkene is found to increase as the bulk of the substituent group cis to the arylthio group increases. We observe, however, very little regioselectivity with respect to which of the mutually perpendicular π bonds of the allene system is attacked, suggesting the presence of an effective mechanism for transmission of inductive effects to the more distant double bond.

scholarly journals Etude par résonance magnétique nucléaire de composés organiques contenant des chalcogènes. II. L'éther de diphényle et ses analogues soufré, sélénié et telluré

1979 ◽  
Vol 57 (22) ◽  
pp. 2967-2970 ◽  
Author(s):  
Gabriel Llabrès ◽  
Marcel Baiwir ◽  
Léon Christiaens ◽  
Jean-Louis Piette
Keyword(s):  
Crystal Structure ◽  
Theoretical Calculations ◽  
Heavy Atom ◽  
Mesomeric Effect ◽  
Heavy Atom Effect ◽  
Inductive Effects ◽  
Structure Determinations ◽  
Résonance Magnétique ◽  
Atom Effect ◽  
Good Agreement

The 1Hmr study of the title compounds has revealed a screw conformation, with defined interconversion processes, in good agreement with crystal structure determinations and theoretical calculations. The mesomeric effect of the heteroatom is smaller than in the anisole series, due to steric inhibitions.The 13Cmr enhances, to some extent, these conclusions. In the case of Te compounds, a heavy atom effect adds to the classical mesomeric and inductive effects to account for the experimental observations.

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