548476-04-6Relevant articles and documents
Isolation and chemistry of aluminum compounds containing (S)-3,3′-bis(triphenylsilyl)-1,1′-bi-2,2′-naphthoxide ligands
Son, Au Ji Ru,Thorn, Matthew G.,Fanwick, Phillip E.,Rothwell, Ian P.
, p. 2318 - 2324 (2003)
The reaction of the resolved, bulky binol (S)-3,3′-bis(triphenylsilyl)-2,2′-dihydroxy-1,1′-binaphthyl, (S)-H2O2C20H10 {SiPh3}2-3,3′ (1), with a variety of alkyl and amide compounds has been investigated. Reaction of 1 with [Al2Me6] initially proceeds only in a 1:1 ratio to produce dinuclear [Al2(O2C20H10{SiPh3} 2-3,3′)(CH3)4], (S)-2. Compound 2 contains a [Al(μ-C)(μ-O)] core, Al-Al = 2.739(2) A, with the binaphthoxide ligand oxygen atoms occupying terminal and bridging positions. In the presence of pyridine, 2 reacts further with 1 to produce [Al(O2C20H10{SiPh3}2- 3,3′)(CH3)(py)], (S)-4. The ethyl analogue of 4, [Al(O2C20H10{SiPh3}2- 3,3′)(CH3)(py)], (S)-5, was obtained from [Et2AlCl]. Both 4 and 5 were shown to adopt tetrahedral geometries in the solid state with O-Al-O angles of ～ 107°. Reaction of [LiAl-(NMe2)4] with 1 produced a dinuclear compound, [LiAl(O2C20H10{SiPh3}2-3, 3′)(NHMe2)- (NMe2)2], (S)-6, containing a terminal and bridging amino group. The lithium-bound HNMe2 ligand could be substituted by pyridine to produce [LiAl(O2C20H10{SiPh3}2-3, 3′) (NC6H5)-(NMe2)2], (S)-7. In the solid state the formally three-coordinated lithium atoms in 6 and 7 are pyramidalized. The sum of the three angles for the LiN2O core is 305° and 322° for 6 and 7, respectively. This is due to an interaction of the lithium with one arene ring of an SiPh3 group. In 6 the carbon atoms involved are an ipso- and ortho-carbon, while for 7 the ortho- and meta-carbon atoms of a Ph-Si ring are in close contact.
