Cyclopentadiene Elimination Reaction as a Route to Bis(neopentyl)gallium Phosphides. Crystal and Molecular Structures of [(Me₃CCH₂)₂GaPEt₂]₂ and [(Me₃CCH₂)₂GaP(C₆H₁₁)₂]₂

Abstract

The compound (Me3CCH2)2Ga(C5H5) has been observed to react at room temperature in pentane solution with HPEt2 and H2P(C6H11) to eliminate C5H6 and form [(Me3CCH2)2GaPEt2]2 and [(Me3CCH2)2GaP(H)(C6H11)]2, respectively. The additional new compound [(Me3CCH2)2GaP(C6H11)2]2 was prepared by a metathetical reaction between Ga(CH2CMe3)2Cl and LiP(C6H11)2 in diethyl ether. All three compounds were fully characterized in solution, whereas two of the three, [(Me3CCH2)2GaPEt2]2 and [(Me3CCH2)2GaP(C6H11)2]2, were characterized by X-ray structural studies.

Monomeric Organogallium−Nitrogen Compounds. Chemistry of Et2GaNH[C6H2(2,4,6-t-Bu)3] with Decomposition to the Metallacycle {EtGaNH[C6H2(4,6-t-Bu)2CMe2CH2-2]}2 and of EtGa{NH[C6H2(2,4,6-t-Bu)3]}2

“…The reagents Et 2 Ga(C 5 H 5 ) and H 2 N[C 6 H 2 (t-Bu) 3 ] have the potential to undergo the cyclopentadiene elimination reaction − to form Et 2 GaNH[C 6 H 2 (t-Bu) 3 ], but no gallium−nitrogen products could be isolated when this reaction was attempted. In contrast, Et 2 Ga(C 5 H 5 ) reacts with many other amines and phosphines at room temperature to form compounds of the type (Et 2 GaER‘ 2 ) n in high purity and in high yield .…”

Facile Reactions for the Preparation of [(Me3CCH2)2GaNH2]2 and of GaN

“…We have investigated the reaction of this yellow dihydronaphthalene gallium(III) intermediate C 10 H 8 [Ga(CH 2 CMe 3 ) 2 ] 2 «2NaCl with anhydrous ammonia because of our interest in the reactions of gallium compounds which have two different organic substituents. 2,3,4 The reactivity of this dihydronaphthalene derivative with ammonia was compared, in turn, with that for Ga(CH 2 CMe 3 ) 3 . Two additional reactions of organogallium compounds are also reported: (1) (4) + NaCl reaction.…”

“…Upon warming to room temperature, this intermediate was converted to gallium(I) clusters (GaR) n ( n = 6−12), GaR 3 , and MCl. We have investigated the reaction of this yellow dihydronaphthalene gallium(III) intermediate C 10 H 8 [Ga(CH 2 CMe 3 ) 2 ] 2 ·2NaCl with anhydrous ammonia because of our interest in the reactions of gallium compounds with two different organic substituents. − The reactivity of this dihydronaphthalene derivative with ammonia was compared, in turn, with that for Ga(CH 2 CMe 3 ) 3 . Two additional reactions of organogallium compounds are also reported: (1) the reaction of the low oxidation state gallium cluster [Ga(CH 2 CMe 3 )] n with ammonia and (2) the reaction of Ga(CH 2 CMe 3 ) 2 Cl with sodium in liquid ammonia.…”

The Dihydronaphthalene Elimination Reaction as a Route to Gallium−Nitrogen Compounds. Crystal and Molecular Structure of [(PhMe2CCH2)2GaNHPh]2

“…Since these reactions provide a direct connection between group 13−15 chemistry and the preparation of electronic materials such as GaN, InN, GaAs, and InP, we have attempted to discover new hydrocarbon elimination reactions which occur at temperatures lower than those typically observed for the simple homoleptic organogallanes and group 15 bases (ER 3-n H n : E = N, P, As; n = 1−3) because lower reaction temperatures minimize the possibility of decomposition reactions and, in turn, should lead to the formation of purer materials. This goal was realized with the discovery of the cyclopentadiene elimination reaction between R 2 Ga(C 5 H 5 ) (R = Me, Et, and CH 2 CMe 3 ) and amines and phosphines. These reactions typically occur below room temperature or 100−200 °C lower than the temperatures needed for reactions of GaR 3 with the same bases.…”

“…The dihydronaphthalene elimination reaction between Na 2 {C 10 H 8 [Ga(CH 2 CMe 2 Ph) 2 Cl] 2 } and aniline was compared directly with the cyclopentadiene elimination reaction between (PhMe 2 CCH 2 ) 2 Ga(C 5 H 5 ) and aniline. The latter was prepared in situ by a stoichiometric ligand redistribution reaction between Ga(CH 2 CMe 2 Ph) 3 and Ga(C 5 H 5 ) 3 . After a stoichiometric amount of aniline was added to the solution of (PhMe 2 CCH 2 ) 2 Ga(C 5 H 5 ), the reaction mixture was maintained at −10 °C, and after 24 h [(PhMe 2 CCH 2 ) 2 GaNHPh] 2 , a slightly soluble solid, was isolated in higher than 70% yield.…”