Synthetic, structural and theoretical studies of amidinate and guanidinate stabilised germanium(I) dimers.
نویسندگان
چکیده
The neutral germanium(i) dimers, [{Ge(Piso)}(2)] and [{Ge(Giso)}(2)], Piso = [(ArN)(2)CBu(t)](-), Giso = [(ArN)(2)CNPr(i)(2)](-), Ar = C(6)H(3)Pr(i)(2)-2,6, which are stabilised by bulky amidinate and guanidinate ligands respectively, have been prepared by reduction of the corresponding germanium(ii) chlorides, [Ge(Piso)Cl] and [Ge(Giso)Cl]; theoretical studies suggest that the Ge-Ge bonds of [{Ge(Piso)}(2)] and [{Ge(Giso)}(2)] are associated with their HOMOs, whilst their LUMOs have substantial Ge-Ge pi-bonding character.
منابع مشابه
Donor Properties of a New Class of Guanidinate Ligands Possessing Ketimine Backbones: A Comparative Study Using Iron.
Addition of 1 equiv of LiN═C(t)Bu2 or LiN═Ad (Ad = 2-adamantyl) to the aryl carbodiimide C(NDipp)2 (Dipp = 2,6-diisopropylphenyl) readily generates the lithium ketimine-guanidinates Li(THF)2[(X)C(NDipp)2] (X = N═C(t)Bu2 (1-(t)Bu), N═Ad (1-Ad)) in excellent yields. These new ligands can be readily metalated with iron to give the N,N'-bidentate chelates [{(X)C(NDipp)2}FeBr]2 (X = N═C(t)Bu2 (5-(t)...
متن کاملSynthesis, characterisation and reactivity of germanium(II) amidinate and guanidinate complexes.
Reactions of lithium salts of the bulky guanidinate ligands, [ArNC(NR2)NAr](-) (NR2 = N(C6H11)2 (Giso-) and cis-NC5H8Me2-2,6 (Pipiso-); Ar = C6H3Pri2-2,6), with GeCl2.dioxane afforded the heteroleptic germylenes, [(Giso)GeCl] and [(Pipiso)GeCl], the former of which was structurally characterised. The further reactivity of these and the related complexes, [(Piso)GeCl] and [(Priso)GeCl] (Piso- = ...
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Reactions of the bulky amidinate and guanidinate salts K[(ArN)(2)CR] (R = Bu(t), NPr(i)(2) or N(C(6)H(11))(2); Ar = 2,6-diisopropylphenyl) with [{RhCl(eta(4)-COD)}(2)] (COD = 1,5-cyclooctadiene) lead to KCl elimination and the formation of the complexes, [Rh{(eta(5)-ArN)(ArN)CR}(COD)], in which the anionic ligand coordinates the rhodium centre in an unprecedented eta(5)-cyclohexadienyl mode. Th...
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متن کاملLow coordinate lanthanide(II) complexes supported by bulky guanidinato and amidinato ligands.
The preparation of a series of homoleptic, four-coordinate lanthanide(ii) complexes, [Ln(Priso)(2)] (Ln = Sm, Eu or Yb) incorporating the bulky guanidinate ligand Priso(-) ([(ArN)(2)CNPr(i)(2)](-), Ar = 2,6-diisopropylphenyl) is described. X-ray crystallography shows the complexes to be isostructural and to exhibit coordination geometries midway between tetrahedral and planar. Comparisons betwe...
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ورودعنوان ژورنال:
- Chemical communications
دوره 38 شماره
صفحات -
تاریخ انتشار 2006