Stilbenediamine complexes

Stibine, tris(dipropyldithiophosphonium)-stereochemistry, 81 Stilbenediamine complexes structure, 25... 

Oren F. Williams and J. C. Bailar, Jr., The Stereochemistry of Complex Inorganic Compounds. XXIV. Cobalt Stilbenediamine Complexes, J. Am. Chem. Soc. 81 4464 (1959). 

One of the most elegant uses of optical activity was the experiment by Mills and Quibell which demonstrated the square planar geometry of Pt(II). They prepared the Pt(II) complex of isobuty-lenediamine and /neso-stilbenediamine and found that it was chiral. If the geometry at platinum is tetrahedral the complex has a mirror plane and so is not chiral, Figure 3.4. 

FIGURE 5.16 Examples of chiral planar complexes (a) cyclometallate ferrocene-Pt, (b) [PtCl3(lra i-2-butene)], and (c) [(meio-stilbenediamine)(isobutyldiamine)Pt]2 +. ... 

Other Applications. Other (/ ,/ )-stilbenediamine derivatives have been used to direct the stereochemical course of alkene dihydroxylation (with stoichiometric quantities of Osmium Tetroxide and epoxidation of simple alkenes with Sodium Hypochlorite and manganese(III) complexes. ... 

FIGURE 9-7 Chiral Isomers of Square-Planar Complexes (meso-stilbenediamine)(iSo-butylenedi-amine)platinum(ll) and palladium(ll). (From W. H. Mills and T. H. H. Quibell, J. Chem. Soc.,... 

Fig. 12.5 Possible structures of meso-stilbenediamine) (isobutylenediamine) palladium(II) and platinum(II) complexes (a) planar structure, optically active (b) tetrahedral structure, optically inactive.

Schiff Bases. An extension of work on VO and UOl" complexes of optically active Schiff bases has resulted in the isolation of two series of titanium complexes of stoicheio-metry. TiOSB and TiOSB,HA [SB = quadridentate Schiff base dianion from sali-cylaldehyde and ( —)-propylenediamine, ( —)-butanediamine, meso-butanediamine, (-)-cyclohexylamine, or (-l-) Stilbenediamine A = CIO4, C2O4, or Cl]. The low solubilities of the complexes and an i.r. band at ca. 800 cm attributable to v(Ti—... 

Well-known examples of the square-octahedral ambivalence are provided by the Lifschitz salts, which are complexes of nickel(n) with substituted ethylenediamines, especially the stilbenediamines, one of which is illustrated in (25-G-VII). Many years ago, Lifschitz and others observed that such... 

FIGURE 9.8 Chiral Isomers of Square-Planar Complexes. (Meso-stilbenediamine)( so-butylenediamine) platinum(ll) and palladium(ll). 

Highly sterically hindered diamines, such as A, A, A, A -tetramethylethylenediamine (tmen) and 1,2-dipiperidinoethane, form stable, mixed-ligand complexes such as M(diket)(tmen)]" which often exhibit dramatic solvatochromic effects. For this reason they have been intensively studied. This is reminiscent of the very early work by Lifschitz and co-workers, who employed the hindered stilbenediamine ligand. 

A novel racemic palladacyclic dimeric complex 136 was resolved via recrystallization of its diastereomeric (3 )-prolinate derivatives 137 and 138 (Scheme 20). The chemistry and resolution of chiral PMeBuTh was studied using 139 and 140. Complex 139 was also used in the resolution of stilbenediamine. The P-chiral phosphine PBuTh(4-BrC6H4) was resolved using 141. ... 

In a classic paper on optically active coordination compounds, Mills and Quibell reported the synthesis of a Pt complex containing one molecule of meso-stilbenediamine (H2N-CHPh-CHPh-NH2) and one molecule of isobutylenedi-amine (H2N-CH2-CMe2-NH2). Also, the complex was successfully resolved into its enantiomers. Determine whether the coordination around the metal ion is tetrahedral or square planar. Also illustrate these modes pictorially. 

The use of metal chelates of five tetradentate 8-ketoamine Schiff bases derived from DL-stilbenediamine and meso-stilbenediamines has been assessed for the separation of Cu(II), Ni(II), Pd(II), and oxovanadium(IV) by capillary column gas chromatography with flame ionization (FID) or microwave-induced plasma atomic emission detection [532]. The linear response for the metal chelates of bis(acetylpivalylmethane)-DL-stilbenediimine was found to extend from 0.86-8.6 ng of complex. For the detection of platinum with microwave-induced plasma atomic emission, the volatile Pt(II) complex of N,N-ethylene-bis(5,5-dimethyl-4-oxohexane-2-imine) can be quantitatively eluted from a GC capillary column [533]. 

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