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Halo, Alkyl, Aryl, and Bis(imido) Complexes of Niobium Supported by the beta-Diketiminato Ligand.

ABSTRACT: 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.

SUBMITTER: Tomson NC

PROVIDER: S-EPMC2909775 | biostudies-literature | 2010 Jun

REPOSITORIES: biostudies-literature

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Halo, Alkyl, Aryl, and Bis(imido) Complexes of Niobium Supported by the beta-Diketiminato Ligand.

Tomson Neil C NC Arnold John J Bergman Robert G RG

Organometallics 20100601 13

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) ...[more]

PMID: 20671985

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Project description:We have investigated both the chemical reduction of (BDI)Nb(V) imido complexes (BDI = HC[C(Me)NAr](2); Ar = 2,6-(i)Pr(2)-C(6)H(3)) to the formal Nb(III) oxidation state and the ability of these Nb(III) complexes to behave as two-electron reductants. The reduction of the Nb(V) species was found to depend heavily on the nature of available supporting ligands, but the chemistry of the reduced compounds proceeded cleanly with a number of unsaturated organic reagents. Accordingly, the novel Nb(V) bis(imido) complexes supported by the monoazabutadiene (mad) ligand (mad)Nb(N(t)Bu)(NAr)(L') (L' = py, thf) were formed by either KC(8) reduction of (BDI)Nb(N(t)Bu)Cl(2)(py) in the absence of strong π-acids or by H(2) reduction of the Nb(V) dimethyl complex (BDI)Nb(N(t)Bu)Me(2) in THF. These products are likely formed though an intramolecular, 2 e(-) reductive C-N bond cleavage, as has been observed previously for related Group 4 systems, suggesting that transient Nb(III) intermediates were present in both cases. In the presence of 1,2-bis(dimethylphosphino)ethane (dmpe), KC(8) reduction of (BDI)Nb(N(t)Bu)Cl(2)(py) was arrested at the Nb(IV) oxidation state to give (BDI)Nb(N(t)Bu)Cl(dmpe), which was characterized by solution-state EPR spectroscopy as a Nb-centered paramagnet with strong coupling to the two equivalent phosphorus nuclei (A(iso){(93)Nb} = 120.5×10(-4) cm(-1), A(iso){(31)P} = 31.0×10(-4) cm(-1), g(iso) = 1.9815). When strong π-acids were used to intercept the thermally unstable Nb(III) complex (BDI)Nb(N(t)Bu)(py) prior to reductive cleavage of the ligand C-N bond, the thermally stable Nb(III) species (BDI)Nb(N(t)Bu)(CX)(2)(L″) (X = O, L″ = py; X = NXyl, L″ = CNXyl; Xyl = 2,6-Me(2)-C(6)H(3)) were obtained in good yields. The Nb(III) complexes (BDI)Nb(N(t)Bu)py, (BDI)Nb(N(t)Bu)(CO)(2)(py) and (BDI)Nb(N(t)Bu)(CO)(2) were subsequently investigated for their ability to serve as two-electron reducing reagents for both metal-ligand multiple bond formation and for the reduction of organic π-systems. The reduction of mesityl azide by (BDI)Nb(N(t)Bu)(py) and diphenylsulfoxide by (BDI)Nb(N(t)Bu)(CO)(2) led to the monomeric bis(imido) and dimeric oxo complexes (BDI)Nb(N(t)Bu)(NMes)(py) and [(BDI)Nb(N(t)Bu)](2)(μ2-O)(2), respectively. MeLi addition to (BDI)Nb(N(t)Bu)(CO)(2)(py) resulted in the formation of a Nb-acylate via methide addition to one of the carbonyl carbons. The acylate product was revealed to have a short Nb-C(acylate) bond distance (2.059(4) Å), consistent with multiple Nb-C bond character resulting from Nb(III) back-bonding into the acylate carbon. The interaction of (BDI)Nb(N(t)Bu)(CO)(2) with two equivalents of 4,4'-dichlorobenzophenone resulted in the clean, quantitative formation of the corresponding pinacol coupling product, but introduction of the ketone in 1: 1 molar ratios resulted in mixtures of the pinacol product and the starting material, suggesting that ketone coordination to the Nb(III) complex may be reversible. Relatedly, addition of 1-phenyl-1-propyne to (BDI)Nb(N(t)Bu)(CO)(2) formed a thermally unstable 1: 1 Nb/alkyne complex, as characterized by NMR and IR spectroscopies; reaction of this species with HCl/MeOH yielded a 2: 1 mixture of 1-phenyl-1-propene and the free alkyne, suggesting a high degree of covalency in the Nb-C bonds.

Dataset Information

Halo, Alkyl, Aryl, and Bis(imido) Complexes of Niobium Supported by the beta-Diketiminato Ligand.

Publications

Halo, Alkyl, Aryl, and Bis(imido) Complexes of Niobium Supported by the beta-Diketiminato Ligand.

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