Interannular Nitrogen‐Lithium Bridges in Ferrocenophanes

Abstract

1,1Ј-Bis(trimethylsilylamino)ferrocene (1) reacts with two equivalents of butyllithium to give the N,NЈ-dilithiated amide (2) which has already served in the synthesis of various 1,n-diaza-[n]ferrocenophanes (n Ն 3). Addition of pyridine affords the dipyridine adduct 3 which could be isolated and characterised in the solid state by X-ray crystallography. An N 2 Li 2 bridge is present in 3, and each lithium atom bears one pyridine ligand. From multinuclear magnetic resonance studies ( 1 H, 7 Li, 13 C, 29 Si, 31 P NMR) it appears that important features of the solid state structure of 3 are retained in solution, in particular in the presence of ether or HMPTA [OϭP(NMe 2 ) 3 ], whereas the structure is likely to be different in

1,3,2‐Diselenaborolanes with an Annelated Dicarba‐closo‐dodecaborane(12) Unit: Synthesis, Molecular Structure and Reactivity

“…[4] The dianion A (used as its lithium salt) has already proved valuable as a versatile ligand in transition metal chemistry [5][6][7][8] and applications in maingroup-element chemistry are also emerging. [9][10][11][12][13][14][15] In our experience, it is preferable to use A after careful isolation [9] to avoid side reactions. Observing these precautions, the cyclic selenasilanes 1 and 2 [9] could be obtained in good yield (Scheme 1) as useful starting materials for further syntheses.…”

Boron, aluminium, gallium, indium and thallium

“…177 The synthesis of mono-and di-gallium amide bridged ferrocenophane complexes by reaction of 1,1 0 -bis(trimethylsilylamino)ferrocene with GaMe 3 or GaEt 3 has been reported and the molecular structures of the ethyl derivative 1,3bis(trimethylsilyl)-2alkyl2pyridine1,3,2diazagalla[3]-ferrocenophane described. 178 Homoleptic aminoalkoxides of gallium (and indium) of the types M 4 {(OC 2 H 4 ) 2 NMe} 6 (M = Ga or In) and [Ga{(OC 2 H 4 ) 3 N}] n , have been prepared and their utility in the sol-gel synthesis is of metal-oxide nanomaterials assessed. 179 The homoleptic gallium complexes [Ga(ROCOCHOCOR) 3 ] (R = Me, Et, i Pr, t Bu and SiMe 3 ) have also been investigated for their potential utility as precursors for Ga 2 O 3 .…”