Synthesis and characterization of transition metal complexes containing novel, unsymmetric tridentate organogallate ligands

Onyiriuka, Emmanuel C.; Storr, Alan

doi:10.1139/v87-231

Cited by 14 publications

(6 citation statements)

References 10 publications

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“…Moreover, the Ga−O bond distances within the molecule (Ga−O(1) = 1.8625(16) and Ga−O(2) = 1.8605(16) Å) are nearly equal. These data compare well with those of the pyridine-stabilized, four-coordinated alkoxide complexes Ga[OCH(CF 3 ) 2 ] 3 (4-Me 2 Npy) and Ga[OCMe 2 (CF 3 )] 3 (4-Me 2 Npy) (∼1.801(5) Å), as well as the alkyl complexes (Bu t ) 2 Ga(OBu t )(OAsPh 3 ) (1.860(6) Å), Me 2 Ga[O(C 5 H 3 N)CH 2 NMe 2 ] (1.892(3) Å), and (Bu t ) 2 GaOR, where R = 2,6-Bu t 2 -4-MeC 6 H 2 (1.821(3) Å) and R = CPh 3 (1.831(4) Å) . The observed donor−acceptor Ga−N distances (Ga−N(1) = 2.1179(19) Å and Ga−N(2) = 2.1301(19) Å) are substantially longer than those of formally covalent Ga−N bonds (1.82−1.94 Å) of the other amide compounds, as summarized by Brothers and Power .…”

Section: Resultssupporting

confidence: 71%

Synthesis and Characterization of Fluorinated Aminoalkoxide and Iminoalkoxide Gallium Complexes: Application in Chemical Vapor Deposition of Ga₂O₃ Thin Films

Chi¹,

Chou²,

Wang³

et al. 2003

Organometallics

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Gallium trichloride, GaCl 3 , reacts with the in situ prepared sodium salt of an aminoalkoxide or iminoalkoxide, denoted as NaL, to give the disubstituted compounds GaL 2 Cl, where L ) OC(CF 3 ) 2 CH 2 NMe 2 (1), OC(CF 3 ) 2 CH 2 C(Me)dNMe (2). Single-crystal X-ray diffraction studies on 1 and 2 indicated the formation of a trigonal-bipyramidal structure with chloride and alkoxy groups occupying the equatorial sites and the nitrogen donors located at the axial positions. For the related trimethylgallium reagent GaMe 3 , addition of an equal amount of amino alcohol LH induced the elimination of methane to afford the complexes GaMe 2 L, where L ) OC(CF 3 ) 2 CH 2 NHMe (3), OC(CF 3 ) 2 CH 2 NHBu t (4), OC(CF 3 ) 2 CH 2 NMe 2 (5), in high yields. The crystal structure of 5 was determined by X-ray diffraction, showing a distortedtetrahedral framework which differs greatly from that observed in the trigonal-bipyramidal Ga complexes 1 and 2. Variable-temperature 1 H NMR studies on 3 and 4 indicated the occurrence of rapid NfGa bond scission, followed by recoordination with a change of the absolute configuration. A lower activation barrier was observed for the Bu t complex 4 upon changing solvents from CDCl 3 to more polar media such as deuterated toluene and THF. Complexes 1 and 4 were then evaluated as potential precursor molecules for the chemical vapor deposition of Ga 2 O 3 , and the as-deposited films were analyzed using scanning electron micrographs (SEM), X-ray photoelectron spectroscopy (XPS), and Rutherford backscattering (RBS).

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Section: Resultssupporting

confidence: 71%

Synthesis and Characterization of Fluorinated Aminoalkoxide and Iminoalkoxide Gallium Complexes: Application in Chemical Vapor Deposition of Ga₂O₃ Thin Films

Chi¹,

Chou²,

Wang³

et al. 2003

Organometallics

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“…A meridional arrangement of the gallate ligands would lead to one signal for each of these groupings if the inversion from the h to 6 conformation of the (OCH2CH2NMe2)M five-membered ring were facile. Such facile inversions have been well documented in our earlier studies (8)(9)(10)(11)(12) and of necessity involve pyramidal inversion at the three-coordinate oxygen atom in the mer structures. However, the 'H nmr spectra of five of the six complexes studied show, even at room temperature, only one signal for the -GaMe2 group, and one signal for the -NMe2 group, where applicable.…”

Section: Resultssupporting

confidence: 66%

Synthesis, characterization, and fluxional behavior in solution of the salts Et₄N⁺[Me₂Ga(N₂C₅H₇)(OCH₂CH₂X)]M(CO)₃⁻ (where N₂C₅H₇ = 3,5-dimethylpyrazolyl, X = NMe₂ or SEt, and M = Cr, Mo, or W). X-Ray crystal structure of the W complex with X = NMe₂

Chong¹,

Rettig²,

Storr³

et al. 1990

Can. J. Chem.

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. Can. J. Chem. 68, 109 (1990). The tricarbonyl anions of Cr, Mo, and W incorporating unsymmetrical tridentate chelating pyrazolyl gallate ligands, [Me2Ga(N2C5H7)(0CH2CH2X)]M(C0)3-, have been isolated as their crystalline E~~N + salts. 'H nmr and solution infrared studies indicate that the octahedral anions display a facial arrangement of the gallate ligand and the three carbonyl groups. This stereochemistry has been proven definitively for the tungsten complex with X = NMe2 by an X-ray structure determination (see below). Fluxional behavior for the anions in d6-acetone solution has been demonstrated by variable temperature 'H nrnr studies and is compared to similar behavior displayed by the neutral molybdenum "allyl" complex, [Me2Ga- Mots ~1 . 4~ : complexes gallate de pyrazole, comportement fluxionnel des complexes Ga-W, structure cristalline d'une complexe Ga-W, complexes Ga-W.[Traduit par la revue]

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“…In solution, 1 exhibits a high ν NO absorption feature in its IR spectrum (1877 cm –1 , CH 2 Cl 2 ). This ν NO value is higher than those observed for previously reported nickel nitrosyls (1568–1867 cm –1 ) ,− and can be attributed to the weak Lewis basicity of CH 3 NO 2 and its overall cationic charge . In contrast, this value is lower than that of [Cu(CH 3 NO 2 ) 5 (NO)][PF 6 ] 2 (1933 cm –1 , CH 3 NO 2 ) .…”

Section: Resultsmentioning

confidence: 51%

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]

Wright

Hayton

2011

Inorg. Chem.

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The reaction of [NO][PF(6)] with excess Ni powder in CH(3)NO(2), in the presence of 2 mol % NiI(2), results in the formation of [Ni(NO)(CH(3)NO(2))(3)][PF(6)] (1), which can be isolated in modest yield as a blue crystalline solid. Also formed in the reaction is [Ni(CH(3)NO(2))(6)][PF(6)](2) (2), which can be isolated in comparable yield as a pale-green solid. In the solid state, 1 exhibits tetrahedral geometry about the Ni center with a linear nitrosyl ligand [Ni1-N1-O1 = 174.1(8)°] and a short Ni-N bond distance [1.626(6) Å]. As anticipated, the weakly coordinating nitromethane ligands in 1 are easily displaced by a variety of donors, including Et(2)O, MeCN, and piperidine (NC(5)H(11)). More surprisingly, the addition of mesitylene to 1 results in the formation of an η(6)-coordinated nickel arene complex, [Ni(η(6)-1,3,5-Me(3)C(6)H(3))(NO)][PF(6)] (6). In the solid state, complex 6 exhibits a long Ni-C(cent) distance [1.682(2) Å], suggesting a relatively weak Ni-arene interaction, a consequence of the strong π-back-donation to the nitrosyl ligand. The addition of anisole to 1 also results in the formation of a η(6) nickel arene complex, [Ni(η(6)-MeOC(6)H(5))(NO)][PF(6)] (7). This complex also exhibits a long Ni-C(cent) distance [1.684(1) Å].

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Synthesis and characterization of transition metal complexes containing novel, unsymmetric tridentate organogallate ligands

Abstract: [Traduit par la revue]

Cited by 14 publications

References 10 publications

Synthesis and Characterization of Fluorinated Aminoalkoxide and Iminoalkoxide Gallium Complexes: Application in Chemical Vapor Deposition of Ga₂O₃ Thin Films

Synthesis and Characterization of Fluorinated Aminoalkoxide and Iminoalkoxide Gallium Complexes: Application in Chemical Vapor Deposition of Ga₂O₃ Thin Films

Synthesis, characterization, and fluxional behavior in solution of the salts Et₄N⁺[Me₂Ga(N₂C₅H₇)(OCH₂CH₂X)]M(CO)₃⁻ (where N₂C₅H₇ = 3,5-dimethylpyrazolyl, X = NMe₂ or SEt, and M = Cr, Mo, or W). X-Ray crystal structure of the W complex with X = NMe₂

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]

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Synthesis and characterization of transition metal complexes containing novel, unsymmetric tridentate organogallate ligands

Abstract: [Traduit par la revue]

Cited by 14 publications

References 10 publications

Synthesis and Characterization of Fluorinated Aminoalkoxide and Iminoalkoxide Gallium Complexes: Application in Chemical Vapor Deposition of Ga2O3 Thin Films

Synthesis and Characterization of Fluorinated Aminoalkoxide and Iminoalkoxide Gallium Complexes: Application in Chemical Vapor Deposition of Ga2O3 Thin Films

Synthesis, characterization, and fluxional behavior in solution of the salts Et4N+[Me2Ga(N2C5H7)(OCH2CH2X)]M(CO)3− (where N2C5H7 = 3,5-dimethylpyrazolyl, X = NMe2 or SEt, and M = Cr, Mo, or W). X-Ray crystal structure of the W complex with X = NMe2

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO2)3][PF6]

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Synthesis and Characterization of Fluorinated Aminoalkoxide and Iminoalkoxide Gallium Complexes: Application in Chemical Vapor Deposition of Ga₂O₃ Thin Films

Synthesis and Characterization of Fluorinated Aminoalkoxide and Iminoalkoxide Gallium Complexes: Application in Chemical Vapor Deposition of Ga₂O₃ Thin Films

Synthesis, characterization, and fluxional behavior in solution of the salts Et₄N⁺[Me₂Ga(N₂C₅H₇)(OCH₂CH₂X)]M(CO)₃⁻ (where N₂C₅H₇ = 3,5-dimethylpyrazolyl, X = NMe₂ or SEt, and M = Cr, Mo, or W). X-Ray crystal structure of the W complex with X = NMe₂

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]