Advanced Propellant Chemistry by Gould R.F. (ed.)

By Gould R.F. (ed.)

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O Despite being heavier than aluminum, gallium is closer to phosphorus both in size and electronegativity (EN) (see Table I). 33 A), and ionic contributions to either the Ga-P or Ga-As bonds are expected to be quite small. rr-bonding in gallium phosphides are Ga-P bond shortening, a low torsion angle, and planarity-or at least flattened pyramidal geometry-at phosphorus. Several of the gallium phosphide structures show both structural and VT NMR 32 PENELOPE J. BROTHERS AND PHILIP P. rr-interaction.

H contacts, and crystal packing forces may influence the flexible M-0-C angles. However, in the bisaryloxides MeA1(0-2,6-t-Bu2-4MeC&2)26 and ~ - B u A ~ ( O - ~ , ~ - ~ -itBis U~ interesting C ~ H ~ ) that , , ~the ~ narrowest angle at aluminum is 0-A1-0, close to 1 11" in both compounds, even though the 0 atoms bear the very bulky substituents. The 0 - A 1 4 angles in both compounds are between 120 and 130". In addition, the planar framework (cf. allene) seen for O[AI{CH(SiMe,)z}2]2'("'b does not strongly support the existence of significant A1-0 T-bonding.

Variable-temperature 'HNMR studies of Me~P{Ga(Trip),);~and t-Bu,GaP(Me~*)SiPh37~*~~ show barriers to rotation around the Ga-P bond of Multiple Bonding Involving Heavier Main Group Elements 33 FIG. 15. Thermal ellipsoidal plot8n of t-Bu2GaP(Mes*)SiPh, showing the flattened nature of phosphorus geometry and the alignment between the gallium p-orbital and the phosphorous lone pair. 7 kcal mol-I, respectively. The latter compound has a higher barrier even though the former has the shorter bond length, again reinforcing the view that bond shortening through n-overlap in some of these compounds might be inhibited by steric factors.

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