Phosphane‐Catalyzed Reactions of LAlH₂ with Elemental Chalcogens; Preparation of [LAl(μ‐E)₂AlL] [E = S, Se, Te, L = HC{C(Me)N(Ar)}₂, Ar = 2,6‐iPr₂C₆H₃]

Addition of catalytic amounts of a phosphane to a reaction mixture containing LAlH 2 [ 2 ; L = HC{C(Me)N(Ar)} 2 , Ar = 2,6‐ i Pr 2 C 6 H 3 ] and elemental Se or Te resulted in the formation of poorly soluble [LAl(μ‐Se) 2 AlL] ( 3 ) and [LAl(μ‐Te) 2 AlL] ( 4 ), respectively. The sulfur analogue [LAl(μ‐S) 2 AlL] ( 5 ) could not be obtained from the direct reaction of 2 with elemental sulfur; consequently, its synthesis was successfully achieved from the reaction of [LAlH 2 ] and [LAl(SH) 2 ]. A possible mechanism for the formation of [LAl(μ‐Se) 2 AlL] and [LAl(μ‐Te) 2 AlL] is discussed. The molecular structures of compounds 3 − 5 were determined by X‐ray structure analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)