Chiral Dimethylindium Aminoalkoxides

Abstract

Chiral dimethylindiumaminoalkoxides of general formula Me21nOR* [OR' = (+);(-)-2piperidyl-methoxy (11, (+);(-)-dimethylamino-2-propoxy (21, (S)-(+)-amino-2-propoxy (31, (3-n, a-diphenyl-2-pyrrolidinyl-methoxy (411 have been prepared by reaction of MeJn with the corresponding aminoalcohols HOR* and characterized by 'H and I3C nmr spectroscopy and X-ray crystallography. Dimeric molecules of 1-4 are composed of two p2-O-bridged chelating rings, the latter formed due to N-In donor-acceptor interaction. This geometry is comparable with that of aluminium and gallium analogues previously investigated. In the case of 1 and 4, the formation of the N-In bond proceeds stereospecifically. The absolute structure of 3 and 4 was confirmed by refinement of the Flack parameter.1: C2/rn; a = 15.999(3) A, b = 9.803(2) A, c = 7.410(1) A, = 111.04(3)"; Z = 2; density (calc.) 2: C2/c; a = 13.184(3) A, b = 9.987(2) A, c = 15.851(3) A, p = 90.66(3)"; Z = 4; density (calc.

Fluorinated Aminoalkoxide and Ketoiminate Indium Complexes as MOCVD Precursors for In2O3 Thin Film Deposition

“…This bond length is also longer than the sum of the covalent radii of N(sp 3 ) and O (2.19 Å) as well as the distance between the indium atom and the amide functional group observed in MeIn[N(CH 2 Ph)(2-NC 5 H 4 )] 2 (2.146−2.169 Å) . Similar distorted trigonal bipyramidal geometry at the indium center has been noted in the closely related aluminum and gallium chiral aminoalkoxide complexes of the type [Me 2 MOR] 2 , where M = Al, R = CHMeCH 2 NMe 2 , CHMeCH 2 NH 2 ; and M = Ga, R = CHMeCH 2 NMe 2 . These structures are also dimeric in the solid state and consist of a central M 2 O 2 rectangle and two five-membered heterocyclic rings located at each of the aluminum or gallium metal atoms.…”

Synthesis and Characterization of Intramolecularly Stabilized Chiral Dimethylindium Alkoxides and their Use as Cross Coupling ReagentsProfessor Joachim Strähle zum 65. Geburtstag gewidmet

“…This effect is best described by a fast association-dissociation process of the amino donor while the In 2 O 2 -ring remains intact, thus maintaining the original nature of the complex. Similar intramolecularly stabilized dialkylmetaloxides of aluminium and gallium show the same dynamic behaviour [6,7]. Since the OCH 2 protons of 3 to 5 (R ϭ H) are diastereotopic (H, HЈ) due to the stereocenter, two doublet-doublet systems with different chemical shifts are to be expected.…”

“…Unless otherwise stated, commercially available amino-acids were used for the preparation of the enantiomerically pure amino alcohols according to known methods [12]. [Me 2 In{µ-O(CH 2 ) 2 NMe 2 }] 2 (1) [13] as well as [Me 2 In{µ-OCH 2 CH(Me)NMe 2 }] 2 (2) [7] were prepared using the reported procedures. The palladium catalysts formed in situ by interacting palladium(II) acetate with either (R,S)-or (S)-bis(diphenylphosphino)-1,1Ј-binaphthalene (binap) were used as previously described [14].…”

“…Quite recently we reported on some chiral, intramolecularly stabilized dimeric organogallium and organoaluminium aminoalcoholates [6], prepared from trimethylaluminium and or trimethylgallium and aminoalkohols. At the same time, Hecht et al could demonstrate that trimethylindium reacts with chiral aminoalkohols in the same way [7]. The present paper reports on the synthesis and the spectroscopic and structural properties of several new dimethylindium complexes stabilized by chiral and achiral chelating ligands and their utilization for the partial kinetic resolution of 2-carbomethoxy-2Ј-(trifluoromethanesulfonyloxy)-1,1Ј-binaphthalene.…”

“…The racemic ester was prepared from the racemic 2,2Ј-bis(trifluorometansulfonyloxy)-1,1Ј-binaphthalene [15], Pd(OAc) 2 , and 1,3-bis(diphenylphosphino)propane in 45 % yield in analogy to the preparation of the R-isomer [16]. Purification of (R,S)-8 was accomplished by plc on silica gel using benzene as eluent [17] (5), CCDC 173794 (6), and CCDC 173795 (7). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: ϩ44-(0)1223-33 60 33 or e-mail: deposit@ccdc.cam-.ac.uk).…”