The isolation and chemistry of group 4, 5, 13 and 14 metal complexes containing resolved (S) and (R)-3,3'-bis(triphenylsilyl)-1,1'-bi-2,2'-naphthoxide ligands

Au Ji Ru Son, Purdue University

Abstract

The reaction of the resolved, bulky BINOL 3,3′-disubstituted-2,2 ′-dihydroxy-1,1′-binaphthyl [H2O 2C20H10(R)-3,3′] (R = SiMe 3, SiMe2Ph, SiMePh2, SiPh3) with a variety of alkyl and amide metal compounds has been investigated. Reaction with [Al2Me6] initially proceeds only in a 1:1 ratio to produce dinuclear [Al2(O2C20H10{SiPh 3}2-3,3′)(CH3)4]. In the presence of pyridine this dinuclear compounds reacts further with the BINOL ligand to produce [Al(O2C20H10{SiPh 3}2-3,3′)(CH3)(py)]. Reaction of [LiAl(NMe2)4] with BINOL also produced a dinuclear compound [LiAl(O2C20H10(SiPh3) 2-3,3′)(NHMe2)(NMe2) 2] containing a terminal and bridging amido group. The lithium-bound HNMe2 ligand could be substituted by pyridine to produce [LiAl(O 2C20H10{SiPh3}2-3,3 ′)(py)(NMe2)2]. Reaction of the tantalum dimethylamide substrates mer, cis-[Ta(NMe 2)2Cl3(HNMe2)] with one equivalent of BINOL leads to the series of amine adducts [Ta(O2C20H 10R2-3,3′)(NHMe2)(NMe 2)2] and [Ta(O2C20H10R 2-3,3′)(NHMe2)(NMe2)Cl] (R = SiMe3, SiMe2Ph, SiMePh2, SiPh3). The amine/amide ligands in [Ta(O2C20H10{SiPh 3}2-3,3′)(NHMe2)(NMe 2)Cl] undergo insertion of CS2 leading to the dimethyldithiocarbamate, (S)-[Ta(O2C20H10-3,3 ′-{SiPh3}2)(CS2NMe2) 2Cl]. Treatment of [Ge(NMe2)4], [Sn(NMe2) 4] and [Sn(NEt2)4] with one equivalent of BINOL affords dialkylamide adducts [M(O2C20H10{SiPh 3}2-3,3′)(NR2) 2] (M = Ge, Sn; R = Me, Ethyl). The amide in the metal complexes undergo insertion of CS2 leading to dialkyldithiocarbamate, (S )-[M(O2C20H10{SiPh3} 2-3,3′)(CS2NR2)2] (M = Ge, Sn; R = Me, Ethyl).

Degree

Ph.D.

Advisors

Rothwell, Purdue University.

Subject Area

Chemistry

COinS