Low coordinate germanium and tin compounds (ArO)2M=E and (ArO)2M=M′Ln M = Ge, Sn; E = S, Se, -NSiMe3 M′ = Cr, W, Fe, Pt [Ar = 2,4,6-tris((dimethylamino)methyl)phenyl-]

The reactions of the divalent species (ArO)(2)M (Ar = 2,4,6-[(CH3)(2)NCH2](3)C6H2; M = Ge, Sn) with either Me3SiN3, elemental S-8, Se or transition metal complexes M'(CO)(n + 1) (M' = Fe, n = 4; M' = Cr, W; n = 5) (Ph3P)(2)Pt . C2H4 have resulted in the isolation of either the new stable formal metallanimines (ArO)(2)M=N-SiMe3, germanethione, -selone (ArO)(2)Ge=E (E = S, Se) (the expected formations of the stannanethione and -selone were not observed), or the (ArO)(2)M=M'(CO)(n), (ArO)(2)M=Pt(PPh3)(2) complexes, respectively. The direct oxidation of the (ArO)(2)M species with various oxidizing agents led to the formation of the corresponding metalloxanes [(ArO)(2)M-O-](2). All of the chalcogenido- and transition metal-metal 14 complexes have been physicochemically and chemically characterized. The reactions of the (ArO)(2)Ge=E (E = S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species (ArO)(2)M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from germaneselone to germanethione. (C) 1998 Elsevier Science S.A. All rights reserved.