NEW PNICTINOGALLANES [H2GAE(SIME3)(2)](3) (E = P, AS) - FORMATION, STRUCTURAL CHARACTERIZATION, AND THERMAL-DECOMPOSITION TO AFFORD NANOCRYSTALLINE GAP AND GAAS
Jf. Janik et al., NEW PNICTINOGALLANES [H2GAE(SIME3)(2)](3) (E = P, AS) - FORMATION, STRUCTURAL CHARACTERIZATION, AND THERMAL-DECOMPOSITION TO AFFORD NANOCRYSTALLINE GAP AND GAAS, Journal of the American Chemical Society, 120(3), 1998, pp. 532-537
The new compounds [H2GaE(SiMe3)(2)](3) (E = P (1), As (2)), the first
authenticated examples of a phosphinogallane and an arsinogallane cont
aining the GaH2 moiety, an prepared via efficient dehydrosilylation fr
om the respective combinations of H3Ga . NMe3 and E(SiMe3)(3) in dieth
yl ether or toluene. Compounds 1 and 2 are characterized by elemental
analysis. NMR, IR, and mass spectrometry. Single-crystal X-ray structu
ral studies show that the molecular structures of 1 and 2 feature a fl
attened six-member ring of alternating Ga and E centers. Both compound
s are reasonably stable at -30 degrees C but spontaneously decompose a
t ambient temperatures, 2 noticeably faster than 1, with the evolution
of HSiMe3, H-2, and E(SiMe3)(3). The pyrolysis of 1 yields nanocrysta
lline GaP while the pyrolysis of solids from decayed 2 results in nano
crystalline GaAs as determined from XRD studies. Under applied pyrolys
is conditions, the thermally accelerated dehydrosilylation of the prec
ursors is accompanied by a side-evolution of CH4 and retention of smal
l quantities of amorphous Si/C phases.