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Chemistry of nitrosyliron complexes supported by a ?-diketiminate ligand.

ABSTRACT: Several nitrosyl complexes of Fe and Co have been prepared using the sterically hindered Ar-nacnac ligand (Ar-nacnac = anion of [(2,6-diisopropylphenyl)NC(Me)](2)CH). The dinitrosyliron complexes [Fe(NO)(2)(Ar-nacnac)] (1) and (Bu(4)N)[Fe(NO)(2)(Ar-nacnac)] (2) react with [Fe(III)(TPP)Cl] (TPP = tetraphenylporphine dianion) to generate [Fe(II)(NO)(TPP)] and the corresponding mononitrosyliron complexes. The factors governing NO transfer with dinitrosyliron complexes (DNICs) 1 and 2 are evaluated, together with the chemistry of the related mononitrosyliron complex, [Fe(NO)Br(Ar-nacnac)] (4). The synthesis and properties of the related cobalt dinitrosyl [Co(NO)(2)(Ar-nacnac)] (3) is also discussed for comparison to DNICs 1 and 2. The solid-state structures of several of these compounds as determined by X-ray crystallography are reported.

SUBMITTER: Tonzetich ZJ

PROVIDER: S-EPMC4603656 | biostudies-literature | 2011 Feb

REPOSITORIES: biostudies-literature

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Chemistry of nitrosyliron complexes supported by a β-diketiminate ligand.

Tonzetich Zachary J ZJ Héroguel Florent F Do Loi H LH Lippard Stephen J SJ

Inorganic chemistry 20110118 4

Several nitrosyl complexes of Fe and Co have been prepared using the sterically hindered Ar-nacnac ligand (Ar-nacnac = anion of [(2,6-diisopropylphenyl)NC(Me)](2)CH). The dinitrosyliron complexes [Fe(NO)(2)(Ar-nacnac)] (1) and (Bu(4)N)[Fe(NO)(2)(Ar-nacnac)] (2) react with [Fe(III)(TPP)Cl] (TPP = tetraphenylporphine dianion) to generate [Fe(II)(NO)(TPP)] and the corresponding mononitrosyliron complexes. The factors governing NO transfer with dinitrosyliron complexes (DNICs) 1 and 2 are evaluated, ...[more]

PMID: 21244036

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Project description:Synthesis of the complex (BDI)Nb(N(t)Bu)Cl(2)py (BDI = HC[C(Me)N(2,6-iPr(2)-C(6)H(3))](2)) was achieved in high yield following the treatment of Nb(N(t)Bu)Cl(3)py(2) with Li(BDI)(OEt(2)). Substitution of the chlorides for fluorides was effected by introducing 2.0 equiv of Me(3)SnF in toluene, providing the pyridine-coordinated difluoride complex (BDI)Nb(N(t)Bu)F(2)py in modest yield. The pyridine ligands from both halide compounds were removed by treatment of the pyridine adducts with B(C(6)F(5))(3), affording the Lewis base-free complexes (BDI)Nb(NtBu)X(2) (X = Cl, F). Additionally, the Lewis base-free dichlorides of the (t)Bu-imido and Ar-imido (Ar = 2,6-(i)Pr(2)-C(6)H(3)) complexes were obtained following treatment of Nb(NR)Cl(3)(dme) (R = tBu, Ar) with Li(BDI)(OEt(2)). The pyridine-coordinated dichloride was alkylated and arylated to form the dimethyl complex (BDI)Nb(N(t)Bu)Me(2) (described previously, see text) and the mono(p-tolyl) complex (BDI)Nb(N(t)Bu)Cl(p-tol), the latter of which was methylated with MeMgBr to yield the mixed alkyl/aryl complex (BDI)Nb(N(t)Bu)Me(p-tol) in good yield. A rare example of a Group 5 bis((t)Bu-imido) species was synthesized in good yield via treatment of (BDI)Nb(N(t)Bu)Cl(2)py with 2.0 equiv of LiNHtBu to form (BDI)Nb(NtBu)(2)py. Exchange of the coordinated pyridine ligand for either pyridine-d(5) or dmap (p-(dimethylamino)pyridine) was shown to occur through a dissociative mechanism, allowing for removal of the coordinated Lewis base by treatment with B(C(6)F(5))(3). The resulting average C(2v)-symmetric tetracoordinate bis(imido) complex (BDI)Nb(N(t)Bu)(2) was characterized in solution by NMR spectroscopy and observed to undergo clean thermal decomposition to yield (BDI(#))Nb(N(t)Bu)(NH(t)Bu) (BDI(#) = H(2)C=C(NAr)CH=C(NAr)Me) over several hours at room temperature. Treatment of the four-coordinate bis(imido) with (t)BuNCO resulted in clean [2 + 2] cycloaddition to yield an oxaazametallacyclobutane complex, which was further observed to extrude (t)BuN=C=N(t)Bu over 12 h at room temperature. The molecular structures of (BDI)Nb(N(t)Bu)Cl(2)py, (BDI)Nb(NAr)Cl(2), (BDI)Nb(N(t)Bu)Me(2), (BDI)Nb(N(t)Bu)Cl(p-tol), (BDI)Nb(N(t)Bu)(2)py, and (BDI)Nb(NtBu)(2)(dmap) were determined crystallographically. Finally, DFT (BP86) geometry optimization calculations on a model complex of the thermally unstable four-coordinate bis(imido) species allowed for identification of the orbital interactions leading to activation of the imido groups through mixing with the BDI frontier orbitals.

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Chemistry of nitrosyliron complexes supported by a ?-diketiminate ligand.

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Chemistry of nitrosyliron complexes supported by a β-diketiminate ligand.

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