Supersilyltrielanes R*(n)EHal(3-n) (E = triel, R* = SitBu(3)): Syntheses, characterization, reactions, structures [1]

Water- and oxygen-sensitive compounds R*EHal(2).D, R*EHal(2) and R*(2)EHal (R* = SitBu(3); E = B, Al, Ga, In, Tl; Hal = F, Cl, Br, I; D = OR2, NR3) ha ve been synthesized by reaction of EHal(3) with NaR* in the absence or pres ence of donors as well as by substitution of D, Hal or R* by other substitu ents, or by reaction of R*E-2-ER*(2) (E = Al, In) with I-2, H-2, AgF2 or HB r. Thermal decomposition of the compounds in solution or in the gas phase l eads to elimination of D from R*EHal(2).D, or of R*Hal from R*EHal(2) and R *(2)EHal, respectively. The dihalides R*EHal(2) act as Lewis acids with res pect to donors OR2 or NR3 (formation of adducts R*EHal(2).D), the monohalid es R*(2)EHal as Lewis bases withrespect to acceptors EHal(3) (formation of R*E-2(+) EHal(4)(-)). Dehalogenations of R*(2)EHal and R*EHal(2) with alkal i metals or NaR* leads to compounds R*E-4(2) (E = Al, In, Tl), R*E-3(2 .) ( E = Al, Ga), R*E-4(3). (E = Al, Ga), R*E-4(4) (E = Al, Ga), R*Ga-6(8), R*In -8(12), (R*B-2(-)), R*Al-2(-), R*Ga-3(2)-, R*Ga-4(3)-, R*Ga-4(4)2-, R*4Tl3C l, or R*6Tl6Cl2. The structures of R*BBr2. Py, R*AlBr2. NEtMe2, (R*AlClOBu) (2), R*2BF as well as R*2ECl (E = B, Al, Ga, Tl) have been determined by X- ray structure analyses.