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Two dinuclear nickel complexes (Et4N)[Ni(mbpa)-Ni(dtcEt)] (1) (dtcEt = diethyldithiocarbamate) and [Ni(dadtEt)Ni(dtcMe)](BPh4) (2) (dtcMe = dimethyldithiocarbamate) have been synthesized as models ...

A linear bis(phosphine) palladium(0) complex with the bulky aryl substituent, tris(2,2″,6,6″-tetramethyl-m-terphenyl-5′-yl (Tmtp), was found to crystallize as a spontaneously resolved homochiral clathrate with toluene molecules.

The germanedithiols Dmp(Ar)Ge(SH)2 [Dmp=2,6-dimesitylphenyl; Ar = Dep (2,6-diethylphenyl) 1a, Tip (2,4,6-triisopropylphenyl) 1b] were synthesized by the reduction of hexathiagermepanes Dmp(Ar)GeS6 and tetrathiagermolanes Dmp(Ar)GeS4 with NaBH4. The treatment of 1awith 2 equiv of potassium hydride afforded the dipotassium germanedithiolate 2.

The first 1,2,3,4,5,6,7-hexathiagermepanes Dmp(Ar)GeS6 [Dmp=2,6-dimesitylphenyl, Ar = Mes, Dep (2,6-diethylphenyl), Tip (2,4,6-triisopropylphenyl)] were synthesized along with 1,2,3,4,5-tetrathiagermolanes by sulfurization of the corresponding dihydrogermanes. The hexathiagermepane Dmp(Tip)GeS6 slowly converted to the tetrathiagermolane with release of elemental sulfur owing to the steric hindrance.

Treatment of an overcrowded diarylgermylene bearing 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl and 2,4,6-triisopropylphenyl groups with tribenzylamine N-oxide gave the corresponding diarylgermanone 4, the first example of a stable germanium-oxygen double-bond compound. Germanone 4 was stable in solution at room temperature for a short time and underwent [2+3]cycloaddition with mesitonitrile oxide, while in the absence of such a trapping reagent 4 gave two diastereomeric intramolecular cyclization products 8 and 9.

Thermolysis of overcrowded 2,3-diphenylgermirenes bearing bulky substituents on the germanium atom in benzene affords the corresponding kinetically stabilized germylenes, the efficient formation of which is evidenced by the trapping experiments with 2,3-dimethyl-1,3-butadiene. This provides a new and mild method for the generation of germylenes.