The new titanium dicarboxylate complex Cp*TiMe(OOC)2py (2) [Cp*=eta5-C5Me5; (OOC)2py = 2,6-pyridinedicarboxylate] has been synthesized. The reaction of complex 2 with water renders [Cp*Ti(OOC)2py]2O (3). The molecular structure of 3 has been studied by X-ray diffraction methods. Complex 2 reacts with isocyanides to yield the respective iminoacyl derivatives Cp*Ti(eta2-MeCNR)(OOC)2py [R=tBu (4), 2,6-dimethylphenyl (xylyl) (5)]. The molecular structure of complex4 has been established by X-ray diffraction. Compound 2 has been employed as a new building block for the preparation of new early-late heterometallic compounds; it reacts with [M(mu-OH)(COD)]2 (M = Rh, Ir) to give the corresponding tetranuclear metallomacrocycle derivatives [Cp*Ti{(OOC)(2)py}(mu-O)M(COD)]2 [M = Rh (6); Ir (7)]. The molecular structure of 6 has been established by X-ray diffraction.
The new tantalum dialkoxide complexes Cp*TaCl 2 (OCH 2 ) 2 py (1), trans-Cp*TaMe 2 (OCH 2 ) 2py (2), and cis-Cp*TaMe 2 (OCH 2 ) 2 py (3) (Cp* ) η 5 -C 5 Me 5 ; (OCH 2 ) 2 py ) 2,6-pyridinedimethoxide) have been synthesized. The molecular structures of complexes 1 and 2 have been studied by X-ray diffraction methods. The reaction of complex 3 with carbon monoxide renders Cp*Ta-(η 2 -Me 2 CO)(OCH 2 ) 2 py (4), while with isocyanides yields the respective azatantalacyclopropanes Cp*Ta(η 2 -Me 2 CNxylyl)(OCH 2 ) 2 py (6) (xylyl ) 2,6-dimethylphenyl) and Cp*Ta(η 2 -Me 2 CN t Bu)(OCH 2 ) 2 py (7). The molecular structure of complex 4 has been established by X-ray diffraction. The coordinated ketone in 4 can be reduced to 2-propanol in the presence of water. On the other hand, compound 3 reacts with triflic acid (HOTf) to render the corresponding cationic derivative [Cp * TaMe(OCH 2 ) 2 py]OTf (8).
A series of new tantalum-digol (digol = diethylene glycolate) complexes TaCp*Cl2(κ3-digol) (1),
TaCp*Me2(κ3-digol) (2), TaCp*ClMe(κ3-digol) (3), and TaCp*Me(OTf)(κ3-digol) (OTf = triflate) (4)
have been synthesized. Treatment of 2 with 1 equiv of H2O·B(C6F5)3 enabled the synthesis of a tantalum-oxo borane-stabilized complex, TaCp*{O·B(C6F5)3}(κ3-digol) (5). Insertion processes into the methyl
groups of complexes 2, 3, and 4 were not observed upon reaction with CO or isocyanides. In contrast,
complex 4 reacted slowly with 1 equiv of xylylisocyanide (xylyl = 2,6-dimethylphenyl) to yield the
dicationic aminocarbene complex [TaCp*{C(Me)NH(xylyl)}(OH2)(κ3-digol)][OTf]2 (6). All products were
characterized by NMR spectroscopy and elemental analysis. The single-crystal structures of 1, 5, and 6
were determined. The molecular structures of 1, 2, 3, and 6 were also determined by means of DFT-based methods.
A series of new tantalum-tbcp [tbcp = 2,2′-thiobis(4,6-dichlorophenolato)] and tantalum-tbop [tbop = 2,2′-thiobis(6-tert-octylphenolato)] complexes [TaCp*Cl2(κ3-tbop)] (1), [TaCp*Cl2(κ3-tbcp)] (2), [TaCp*Me2(κ3-tbop)] (3), [TaCp*Me2(κ3-tbcp)] (4), [TaCp*Me(κ3-tbop)(OTf)] (OTf = triflate) (5), [TaCp*Me(κ3-tbcp)(OTf)] (6), [TaCp*(κ3-tbop)(OTf)2] (7), and [TaCp*(κ3-tbcp)(OTf)2] (8) have been synthesized. Insertion processes into the methyl groups of complex 3 were not observed upon reaction with CO or isocyanides. In contrast, complex 4 reacted slowly with 1 equiv of xylyl isocyanide (xylyl = 2,6-dimethylphenyl) or tert-butyl isocyanide to yield complexes [TaCp*(κ2-Me2CNxylyl)(κ3-tbcp)] (9) and [TaCp*Me(κ2- MeCNtBu)(κ3-tbcp)] (10), respectively. All products were characterized by NMR spectroscopy and elemental analysis. The single-crystal structures of 2, 3, 6, and 9 were also determined.
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