β-Substitution de la méso-tétraphénylporphyrine de zinc par voie électrochimique

1991 ◽  
Vol 69 (7) ◽  
pp. 1161-1165 ◽  
Author(s):  
Alain Giraudeau ◽  
Lana El Kahef
Keyword(s):  
Carbon Atom ◽  
Nucleophilic Substitution ◽  
Key Words ◽  
Electrochemical Oxidation ◽  
Electrochemical Reactions

The electrochemical oxidation of the zinc tetraphenylporphyrin complex in a mixed acetonitrile–dichloroethane solution in the presence of nucleophiles (Py, 3-Pic, [Formula: see text], SCN−) leads to the formation of the corresponding monosubstituted metalloporphyrin. For each of these nucleophiles the substitution occurs at a pyrrole carbon atom (β-substitution). The electrochemical conditions of these substitutions are discussed and an overall reaction is proposed. Key words: porphyrins, electrochemical reactions, nucleophilic substitution.

ChemInform Abstract: Nucleophilic Substitution at the Central Allyl Carbon Atom of a (π- Allyl)platinum Complex.

ChemInform ◽  
2010 ◽  
Vol 25 (36) ◽  
pp. no-no
Author(s):  
K. OHE ◽  
H. MATSUDA ◽  
T. MORIMOTO ◽  
S. OGOSHI ◽  
N. CHATANI ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Nucleophilic Substitution ◽  
Platinum Complex

Heteroleptic gold complexes with 4,5-diselenolate-1,3-dithiole-2-thione (C3C3Se22-, dsit)

1998 ◽  
Vol 76 (7) ◽  
pp. 1033-1037
Author(s):  
Elena Cerrada ◽  
Mariano Laguna
Keyword(s):  
Key Words ◽  
Electrochemical Oxidation ◽  
Room Temperature ◽  
Zinc Complex ◽  
Trinuclear Complex ◽  
Gold Complexes ◽  
Electrical Conductivities ◽  
Tin Complexes ◽  
Ligand Transfer

The reaction of (NBu4)2[Zn(dsit)2] (dsit = 4,5-diselenolate-1,3-dithiole-2-thione) with AuClL in a 1:4 ratio leads to [Au2(dsit)L2] (L = PPh3 (1), PPh2Me (2)), transferring the diselenolate group. Complex 2 reacts further with equimolar amounts of [Au(OClO3)L], affording the trinuclear complex [Au3(dsit)(PPh2Me)3]ClO4 (3). When the reaction of (NBu4)2[Zn(dsit)2] with [Au2Cl2(P-P)] was carried out in a 1:2 ratio, complexes [Au2(dsit)(P-P)]n (P-P = dppe (1,2-bis(diphenylphosphine)ethane), n = 1 (4); P-P = dppm (bis(diphenylphosphine)methane), n = 2 (5)) are obtained. Anionic derivatives such as (NBu4)[Au(dsit)2] (6) could be obtained by reaction of the zinc complex with (NBu4)[AuBr4] in a 1:1 ratio while other gold complexes require a tin complex as ligand transfer. So [Sn(dsit)Me2] (7), obtained from the zinc complex and [SnCl2Me2], reacts with PPN[Au(C6F5)Cl] (PPN = bis(triphenylphosphine)iminium) or [AuBr2(S2CNR2)] affording [Au(dsit)(S2CNR2)] (R = Me (8); R = Bz (9)) or (PPN)2[Au2(dsit)(C6F5)2] (10), respectively. Electrochemical oxidation of 6 gives (NBu4)0.4[Au(dsit)2] (11) and the reaction with (TTF)3(BF4)2 (TTF = tetrathiafulvalene) affords (TTF)[Au(dsit)2] (12). Electrical conductivities of these complexes at room temperature in compacted pellets are 3 × 10-8 (11) and 5 × 10-3 (12) S cm-1.Key words: diselenolate, dsit, gold complexes, tin complexes.

2-Azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis and nucleophilic substitution at the carbon–nitrogen double bond

1996 ◽  
Vol 74 (3) ◽  
pp. 287-294 ◽  
Author(s):  
Antonio Lorente ◽  
Marta Casillas ◽  
Pilar Gomez-Sal ◽  
Antonio Manzanero
Keyword(s):  
Double Bond ◽  
Nucleophilic Substitution ◽  
Key Words ◽  
Sodium Methoxide ◽  
Stereoselective Synthesis ◽  
X Ray Diffraction ◽  
Key Words 2 ◽  
X Ray ◽  
Nitrogen Double Bond

The synthesis of (E)-1-methoxy-2-azabuta-1,3-diene-4-carbonitriles was performed by methylation of N-alkenylamides 9 and 11. The Z isomers were obtained by treatment of (E)-1-methylthio-2-azabuta-1,3-diene-4,4-dicarbonitriles with sodium methoxide in methanol. We also describe the reactions of (E)-1-methylthio-2-azabuta-1,3-diene-4,4-dicarbonitriles with pyrrolidine, which afforded 1-(1-pyrrolidinyl) derivatives 20, 21, and 23. X-ray crystallographic analyses of 21 and 23 established the E stereochemistry of the C—N double bond. Key words: 2-azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis, nucleophilic substitution and X-ray diffraction; N-alkenylamides: methylation.

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