“…Details of the data collection are listed in Table 1, and selected interatomic distances and angles are listed in Table 2. 6,8,9,11,12,15 The Ga-N bond pair associated with the orthometalated rings is longer than that of the other set of Ga-N bond distances. This fact coupled with the internal angles Ga(1)-N(2)-Ga(1A) ) 89.3(1)°and N(2)-Ga(1)-N(2A) ) 90.7(1)°reveals that the four-membered Ga 2 N 2 core possesses a slightly distorted square geometry.…”
Monitoring the thermolysis reaction of Me 3 Ga with HN(CH 2 Ph) 2 in toluene with multinuclear NMR spectroscopy indicates the initial formation of [Me 2 GaN(CH 2 Ph) 2 ] 2 via 1,2elimination of CH 4 followed by additional 1,2-elimination steps that give the orthometalated gallium dimer [MeGaN(CH 2 C 6 H 4 )(CH 2 Ph)] 2 in 65% yield. This is the first reported example of orthometalation of an aromatic ring carbon by gallium. Because [MeGaN(CH 2 C 6 H 4 )(CH 2 Ph)] 2 forms prior to the complete conversion of (PhCH 2 ) 2 NH‚GaMe 3 to [Me 2 GaN(CH 2 Ph) 2 ] 2 , thermolysis of a Me 3 Ga/HN(CH 2 Ph) 2 mixture is not a viable route to [Me 2 GaN(CH 2 Ph) 2 ] 2 . Instead it was prepared by a salt elimination reaction. The single-crystal X-ray diffraction analysis establishes the dimeric nature of the orthometalated compound and indicates a structure that is consistent with the NMR chemical shift assignements obtained using both 1-D and 2-D NMR techniques.
“…Details of the data collection are listed in Table 1, and selected interatomic distances and angles are listed in Table 2. 6,8,9,11,12,15 The Ga-N bond pair associated with the orthometalated rings is longer than that of the other set of Ga-N bond distances. This fact coupled with the internal angles Ga(1)-N(2)-Ga(1A) ) 89.3(1)°and N(2)-Ga(1)-N(2A) ) 90.7(1)°reveals that the four-membered Ga 2 N 2 core possesses a slightly distorted square geometry.…”
Monitoring the thermolysis reaction of Me 3 Ga with HN(CH 2 Ph) 2 in toluene with multinuclear NMR spectroscopy indicates the initial formation of [Me 2 GaN(CH 2 Ph) 2 ] 2 via 1,2elimination of CH 4 followed by additional 1,2-elimination steps that give the orthometalated gallium dimer [MeGaN(CH 2 C 6 H 4 )(CH 2 Ph)] 2 in 65% yield. This is the first reported example of orthometalation of an aromatic ring carbon by gallium. Because [MeGaN(CH 2 C 6 H 4 )(CH 2 Ph)] 2 forms prior to the complete conversion of (PhCH 2 ) 2 NH‚GaMe 3 to [Me 2 GaN(CH 2 Ph) 2 ] 2 , thermolysis of a Me 3 Ga/HN(CH 2 Ph) 2 mixture is not a viable route to [Me 2 GaN(CH 2 Ph) 2 ] 2 . Instead it was prepared by a salt elimination reaction. The single-crystal X-ray diffraction analysis establishes the dimeric nature of the orthometalated compound and indicates a structure that is consistent with the NMR chemical shift assignements obtained using both 1-D and 2-D NMR techniques.
“…The weaker amine with the more acidic proton reacted fastest. It is also of interest that neophylgallium(III) compounds are stronger Lewis acids than are the corresponding neopentyl derivatives. …”
Section: Resultsmentioning
confidence: 99%
“…All compounds described in this investigation were very sensitive to oxygen and moisture and were manipulated by using standard vacuum line techniques or a purified argon atmosphere in a Vacuum Atmospheres drybox equipped with a Dry Train. The starting compounds Ga(CH 2 CMe 3 ) 3 , Ga(CH 2 CMe 2 Ph) 3 , Ga(CH 2 CMe 3 ) 2 Cl, and Ga(CH 2 CMe 2 Ph) 2 Cl 6 were prepared by using literature methods. All solvents were purified before use.…”
The dihydronaphthalene elimination reaction between Na2[C10H8(GaR2Cl)2}] (R = CH2CMe3, CH2CMe2Ph) and t-BuNH2 provided a room-temperature route to [R2GaNH(t-Bu)]2.
However, when Ga(CH2CMe2Ph)3 and t-BuNH2 were reacted at 140−150 °C, C6H5CMe3 was
eliminated and the product was
a gallium(III) amide with one GaC4 metallocyclic ring, rather than [(PhMe2CCH2)2GaNH(t-Bu)]2. X-ray
structural studies confirmed the identity of this novel compound as well as that of the typical
dimer. When the reaction temperature was increased to 210−230 °C, the product was
a species with two GaC4 metallocyclic
rings.
“…The cross-ring distances associated with the Ga 2 N 2 molecular core are Ga(1)···Ga(1A) = 3.008 Å and N(3)···N(3A) = 2.815 Å (3.018 and 2.780 Å, respectively, for the second molecule). These data may be compared with the corresponding data for the closely related compound [(PhMe 2 CCH 2 ) 2 GaNH( n -Pr)] 2 . The Ga−N distances were slightly shorter at 2.013(2) and 2.029(2) Å, and the Ga 2 N 2 molecular core was slightly more compact, with the two Ga atoms separated by 2.938(1) Å and the two nitrogen atoms by 2.776(3) Å.…”
mentioning
confidence: 94%
“…Three gallium nitrogen compounds, [(PhMe 2 CCH 2 ) 2 GaNHR] 2 (R = H, n -Pr, Ph), were prepared and characterized in this study, but only [(PhMe 2 CCH 2 ) 2 GaNHPh] 2 was characterized by an X-ray structural determination. The products formed at room temperature have sharper and slightly higher melting points and are probably more pure than those formed in sealed tubes at 140−150 °C.…”
The dihydronaphthalene derivative Na2{C10H8[Ga(CH2CMe2Ph)2Cl]2} reacts at room
temperature with NH3, n-PrNH2, and PhNH2 in THF solution to give high yields of [(PhMe2CCH2)2GaNHR]2 (R = H, n-Pr, Ph), C10H10, and NaCl. In contrast, the elimination reactions
between Ga(CH2CMe2Ph)3 with these same amines to form [(PhMe2CCH2)2GaNHR]2 and
PhCMe3 require temperatures of 150 °C. The cyclopentadiene elimination reaction between
(PhMe2CCH2)2Ga(C5H5) and aniline occurs at −10 °C and is the fastest of these three. An
X-ray structural study of [(PhMe2CCH2)2GaNHPh]2 identified it as the trans isomer.
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