Author: Rodolphe Kinghat

1,3-Dipolar cycloaddition of diaryldiazomethanes across N-ethoxy-carbonyl-N-(2,2,2-trichloroethylidene)amine and reactivity of the resulting 2-azabutadienes towards thiolates and cyclic amides

Abstract 1,3-dipolar cycloaddition of diaryldiazomethanes Ar2C N2 across Cl3C–CH N–CO2Et 1 yields Δ3-1,2,4-triazolines 2. Thermolysis of 2 leads, via transient azomethine ylides 3, to diaryldichloroazabutadienes [Ar(Ar')C N–CH CCl2] 4. Treatment of 4a (Ar = Ar' = C6H5) and 4c (Ar = Ar' = p-ClC6H4) with NaSR in DMF yields 2-azabutadienes [Ar2C N–C(H) C(SR)2] 5. In contrast, nucleophilic attack of NaStBu on 4 affords azadienic dithioethers [Ar2C N–C(StBu) C(H)(StBu)] (7a Ar = C6H5; 7b Ar' = p-ClC6H4). The reaction of 4a with NaSEt conducted in neat EtSH produces [Ph2C N–C(H)(SEt)–CCl2H] 8, which after dehydrochloration by NaOMe and subsequent addition of NaSEt is converted to [Ph2C N–C(SEt) C…

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Mono- and di-nuclear 2,3-diazabutadiene and 2-azabutadiene complexes of Rhenium(I): Syntheses, luminescence spectra and X-ray structures

Abstract Treatment of [Re(CO)3(THF)(μ-Br)]2 with 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene [Cl2C C(H)–N CPh2] (1a) yields the di-nuclear benzophenone azine-bridged compound [(OC)3Re(μ-Ph2C N–N CPh2)(μ-Br)2Re(CO)3] (2a), albeit in low yield. Alternatively, compounds [(OC)3Re(μ-Ph2C N–N CPh2)(μ-X)2Re(CO)3] (2a,b) (X = Br, Cl) are obtained in high yields by direct reaction of [Re(CO)3(THF)(μ-Br)]2 or [Re(CO)5Cl] with benzophenone azine. Nucleophilic attack of NaSPh on 1a affords the 2-azabutadiene derivative [(PhS)(Cl)C C(H)–N CPh2] (1b), which upon reaction with [Re(CO)3(THF)(μ-Br)]2 forms the S,N-chelate complex fac-[(OC)3ReBr{(PhS)(Cl)C C(H)–N CPh2}] (3). The crystal structures of 1b, 2…

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4,4-Bis(4-methylphenylsulfanyl)-1,1-diphenyl-2-azabuta-1,3-diene

In the title compound, C29H25NS2, both the Cl atoms of the azadiene precursor 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene are replaced by two vicinal S-p-tolyl substituents attached to the terminal C atom of a π-conjugated 2-azabutadiene array. The azadiene chain is planar to within 0.01 Å. One of the phenyl rings seems to be slightly π-conjugated with the azadiene core [dihedral angle 5.1 (2)°].

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