Bidentate amines

Abbreviations py = pyridine en = ethylenediamine Mejen = l r,i f-dimethyl-ethylenediamine EtenEt = JV,JV -diethylethylenediamine bipy = 2,2 -bipyridine Et4dien = JVfJV,JV, Ar,-tetraethyldiethylenetriamine 4,7-diphenylphen - 4,7-di-phenyl-l,10-phenanthroline tripyam = tri(2-pyridyl)amine (bidentate) dppa = phenyldi(2-pyridyl)amine trien — triethylenetetramine. 

The assumed transition state of this reaction is shown in Scheme 5.3. Yb(OTf)3, (J )-(-h)-BINOL, and DBU form a complex with two hydrogen bonds, and the axial chirality of (J )-(-h)-BINOL is transferred via the hydrogen bonds to the amine parts. The additive would interact with the phenolic hydrogen of the imine, which is fixed by bidentate coordination to Yb(III). Because the top face of the imine is shielded by the amine, the dienophiles approach from the bottom face to achieve high levels of selectivity. 

Bidentate binding of two Lewis acidic boron centers to one methoxide anion was first reported in 1967 [241]. Further examples did not appear until 1985 [242]. Today, other bis(boronates) like 152 and 154-158 (Fig. 41) are known that can be applied to the selective complexation of amines and diamines [243-247]. 

Phosphinous amides, based on proline and tetrahydroisoquinoline carboxylic acid, bearing a second donor center (50, Ar=Ph R =H, CH3,Tr, Ph R =H, CH3,Tr, Ph and 51, R =H,Tr R =H,Tr) (Scheme 40) have been developed for use in allylic alkylation and amination of substituted propenyl acetates, yielding the corresponding products in 87-98% (5-94% ee) and 29-97% (14-93% ee) respectively [55, 167]. With bidentate ligands of type 38 where R=(S)-PhMeCH, and with the bis(aminophosphanes) 52 (R=Ph) similar allylic alkylations have been also tested [168,169]. 

Other dichloro(ditertiary phosphine)nickel(II) complexes (see Table VI) catalyze both hydrosilylation and H/Cl exchange, but analogous complexes containing monodentate phosphine ligands or bidentate amine groups are essentially inactive (173). 

NiS4 core is conserved giving trans octahedral complexes, while with bidentate amines cis octahedral complexes are obtained. Linear bidentate amines can result in a ID chain like in compound (341) where 4,4 -bipyridine molecules bridge the square planar units. 

A number of differently substituted A-(thiocarbamoyl)benzamidines (521) (R = Et, Bu NR2 = morpholino) have been complexed with Ni11. The ligands function in a bidentate manner, coordinating via the primary amine N and thione S atoms.1371... 

Polymeric or monomeric complexes are formed in the reaction between zinc halides and dimethyl(aminomethyl)phosphine oxide dependent on the ratio of reactants. The ligand can bind as bidentate to one metal center or bridge two metal centers through the amine N and phosphine oxide O atoms.851... 

The reactions of mercury(II) salts with oligo-amines afford informative examples for the fact that counterions induce the formation of a distinct complex or select a distinct complex in an equilibrium to crystallize with. Thus, Hg11 acetate with dien under exactly the same reaction conditions, in the presence of C104- or PF6-, yields the dinuclear complex [Hg2(dien)3](C104)4 or the mononuclear species [Hg(dien)(H20)](PF6)2, respectively, both characterized by IR, H, and 13C NMR spectrometries, by fast-atom bombardment (FAB) MS, cyclovoltammetry, and X-ray structure analyses.209 In the first compound Pna2, Z = 4), one Hg adopts five-coordination with one tridentate and one bidentate dien ligand, which with the remaining N-donor binds to the... 

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