First Example of an Aluminum-Phosphorus-Arsenic Mixed-Pnicogen Ring Compound: X-ray Crystal Structure of Et2AlP(SiMe3)2Al(Et)2As(SiMe3)2

Density-Functional Study of the Geometries, Stabilities, and Bond Energies of Group III−V (13−15) Four-Membered-Ring Compounds

“…During the past decade, there has been considerable effort centered on the preparation of potential single-source precursors to various group III-V (13-15) semiconductor and electronic materials. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] As a result, four-membered-ring compounds containing cores of the form MEME (M ) Al, Ga, or In; E ) P or As), 1-12,14-15,18 MEME′ (M ) Al, Ga, or In; E ) As; E′ ) P), [19][20][21] and MEMX (M ) Ga or In; E ) P or As; X ) Cl) (M ) Ga; E ) As; X ) Br) 4,12-17 have been synthesized. Of particular interest are nanometer-size crystallites of semiconductor materials which have interesting properties as a result of quantum confinement effects not observed in bulk material.…”

“…During the past decade, there has been considerable effort centered on the preparation of potential single-source precursors to various group III−V (13−15) semiconductor and electronic materials. − As a result, four-membered-ring compounds containing cores of the form MEME (M = Al, Ga, or In; E = P or As), − ,−, MEME‘ (M = Al, Ga, or In; E = As; E‘ = P), − and MEMX (M = Ga or In; E = P or As; X = Cl) (M = Ga; E = As; X = Br) 4,12-17 have been synthesized. Of particular interest are nanometer-size crystallites of semiconductor materials which have interesting properties as a result of quantum confinement effects not observed in bulk material. − Among such materials, group III−V semiconductors are especially important because of their utility in high-speed digital circuits, microwave devices, and optoelectronics. , One avenue of synthesis for group III−V nanocrystals involves the thermal decomposition of suitable single-source precursors and, to this end, it has been recently demonstrated that the compounds [X 2 GaP(SiMe 3 ) 2 ] 2 (X = Cl, Br, or I) undergo thermolysis at relatively low temperatures to yield nanocrystalline gallium phosphide (GaP) 5 .…”

“…Four-membered-ring compounds containing several different ligands (R, R‘) have been synthesized and characterized by single-crystal X-ray crystallography. − The four-membered-ring compounds studied here are divided into two groups: compounds containing two pnicogens of the general form R 2 ME(R‘) 2 M(R) 2 E‘(R‘) 2 (M = In, ,,− ,,,, Ga, − ,,, Al; ,,− ,, E, E‘ = P, As) and compounds containing one halogen and one pnicogen of the general form R 2 ME(R‘) 2 M(R) 2 X (M = In, ,, Ga; , E = P, As; X = Cl, Br). In our theoretical investigation we consider the case of R, R‘ = H (Figures and ).…”

Small Inorganic Rings in the 21st Century: From Fleeting Intermediates to Novel Isolable Entities

“…By taking advantage of the Lewis acidic nature of many Al(III) compounds, Schulz and co-workers prepared the basestabilized iminoalane dimers [Me 3 N•HAl(μ-NDipp)] 2 (204) and [Me 2 EtN•HAl(μ-NDipp)] 2 (205) from the equimolar reaction between H 3 Al•NMe 2 R (R = Me and Et) and DippNH 2 , with extrusion of molecular hydrogen as a byproduct (Figure 10). 147 Following a similar approach, the related heterocycles [DMAP•Cp*Al(μ-NSiEt 3 )] 2 (206), [DMAP• Cp*Al(μ-NSi i Pr 3 )] 2 (207), and [DMAP•Cp*Al(μ-NSi t BuMe 2 )] 2 (208) were synthesized. 154 Uhl and co-workers reported that hydroalumination of PhCN and Cl 3 CCN with di-tert-butylaluminum hydride or the corresponding diethyl analogue, Et 2 AlH, yielded the products [ t Bu 2 Al(μ-N C(Ph)H)] 2 (209), [Et 2 Al(μ-NC(Ph)H)] 2 (210), and [ t Bu 2 Al(μ-NC(CCl 3 )H)] 2 (211), all of which form dimers possessing planar Al 2 N 2 cores with two exocyclic CN double bonds.…”

“…207 An interesting mixed pnictogen Al−P−Al−As heterocycle, [Et 2 Al(μ-P(SiMe 3 ) 2 )AlEt 2 (μ-As(SiMe 3 ) 2 )] (305) (Figure 13) was synthesized by equilibration of a 1:1 mixture of [Et 2 AlP(SiMe 3 ) 2 ] 2 (306) and [Et 2 AlAs(SiMe 3 ) 2 ] 2 (307) at 45 °C under ultrasonic conditions. 208 The Schnockel group described the green-colored triplet biradical [( t Bu 2 P)Al(μ-P t Bu 2 )] 2 (308), which formally possesses unpaired spin density at each Al(II) site. This product was isolated from the reaction of metastable AlCl with Li[P t Bu 2 ] (Scheme 15); the formation of 308 is thought to proceed by in situ generation of "AlCl 2 " via disportionation of AlCl, which is intercepted by the di-tert-butyl phosphide anion.…”