Homoleptic organoderivatives of high-valent nickel(III).

Homoleptic perhalophenyl derivatives of divalent nickel complexes with the general formula [NBu(4)](2)[Ni(II)(C(6)X(5))(4)] [X=F (1), Cl (2)] have been prepared by low-temperature treatment of the halo-complex precursor [NBu(4)](2)[NiBr(4)] with the corresponding organolithium reagent LiC(6)X(5). Compounds 1 and 2 are electrochemically related by reversible one-electron exchange processes with the corresponding organometallate(III) compounds [NBu(4)][Ni(III)(C(6)X(5))(4)] [X=F (3), Cl (4)]. The potentials of the [Ni(III)(C(6)X(5))(4)](-)/[Ni(II)(C(6)X(5))(4)](2-) couples are +0.

Synthesis and characterization of new five-coordinate platinum nitrosyl derivatives: density functional theory study of their electronic structure.

The neutral, five-coordinate platinum nitrosyl compounds [Pt(C(6)F(5))(3)(L)(NO)] (2) [L=CNtBu (2 a), NC(5)H(4)Me-4 (2 b), PPhMe(2) (2 c), PPh(3) (2 d) and tht (2 e)] have been prepared by the reaction of [NBu(4)][Pt(C(6)F(5))(3)(L)] (1) with NOClO(4) in CH(2)Cl(2). The ionic compound [N(PPh(3))(2)][Pt(C(6)F(5))(4)(NO)] (4) has been prepared in a similar way starting from the homoleptic species [N(PPh(3))(2)](2)[Pt(C(6)F(5))(4)] (3). Compounds 2 and 4 are all diamagnetic with [PtNO](8) electronic configuration and show nu(NO) stretching frequencies at around 1800 cm(-1).

A new series of homoleptic, paramagnetic organochromium derivatives: synthesis, characterization, and study of the magnetic properties.

The synthesis and characterization of the triad of organochromium derivatives [Cr(C(6)Cl(5))(4)](n-) (n=0, 1, 2) are described. By treating [CrCl(3)(thf)(3)] with LiC(6)Cl(5) in 1:5 molar ratio, the salt [Li(thf)(4)][Cr(III)(C(6)Cl(5))(4)] (1) was obtained as a violet solid in 57 % yield. Oxidation of 1 with [N(4-BrC(6)H(4))(3)][SbCl(6)] yielded the neutral complex [Cr(IV)(C(6)Cl(5))(4)] (2) as a brown solid in 71 % yield.