Reactivity of Me3M (M=Al, Ga, In) with benzylamine to form the dimers, [Me2MN(H)CH2Ph]2, and the hexamers, [MeAlNCH2Ph]6 and [MeGaNCH2Ph]6: molecular structures of trans-[Me2MN(H)CH2Ph]2 and [MeAlNCH2Ph]6

Synthesis and Molecular Structure Studies of [Me2AlN(i-Pr)CH2Ph]2 and the Related Orthometalated Dimers [RAlN(i-Pr)-μ-(CH2C6H4)]2, where R = Me, n-Pr, n-Bu, i-Bu

“…These data are consistent with those reported for cis -[Me 2 AlN(H) i -Pr] 2 , cis -[Me 2 AlN(Me)CH 2 Ph] 2 , and [Me 2 AlN(C 6 H 11 ) 2 ] 2 , with fold angles of 15.5°, 20.4°, and 27.4°, respectively. The molecular structure data for 1a are in agreement with published data and correlations of the steric properties of functional groups attached to the amine nitrogen with the corresponding dimer geometries. ,,− ,− …”

“…Our results are in agreement with those of Bradley 10 in that the influence of R‘ is more important than that of R and that the effect is primarily steric in nature. Mass spectral studies on the related series [Me 2 InNR‘ 2 ] 2 and on [Me 2 AlN(CH 2 Ph) 2 ] 2 and [Me 2 AlN(H)CH 2 Ph] 2 , suggest that the dimers become less stable in the vapor phase with increasing steric bulk of the R‘ group.…”

“…Also, [R 2 AlN(Me)CH 2 Ph] 2 is readily formed from the thermolysis of R 3 Al/HN(Me)CH 2 Ph mixtures, but the corresponding orthometalated dimers are obtained from these reaction mixtures only at high temperatures and very long heating times . The thermolysis reaction of Me 3 Al with the primary amine H 2 NCH 2 Ph, where R‘ = H instead of benzyl, at 135 °C results in the formation of the hexameric cage compound [MeAlNCH 2 Ph] 6 , rather than the orthometalated dimer.…”

“…1 H and 13 C NMR Data. The 1 H and 13 C NMR chemical shift assignments for 1 − 5 were made using a combination of 1D and 2D NMR techniques and the procedures established for the NMR chemical shift assignments of [Me 2 AlN(H)CH 2 Ph] 2 , [R 2 AlN(CH 2 Ph) 2 ] 2 , , [RAlN(CH 2 Ph)-μ-(CH 2 C 6 H 4 )] 2 , and [RAlN( t -Bu)-μ-(CH 2 C 6 H 4 )] 2 . The 1 H and 13 C NMR spectra of [Me 2 AlN( i -Pr)CH 2 Ph] 2 ( 1 ) indicate the presence of both cis ( 1a ) and trans ( 1b ) isomers with respect to the Al 2 N 2 ring in benzene- d 6 solution at RT in a 60:40 cis/trans isomer ratio.…”