scholarly journals Complexes of Antimony(III)

2015 ◽  
Vol 4 ◽  
pp. 45-48
Author(s):  
Ram Nath Prasad Yadav

Lewis acidity of antimony(III) halides and their organo substituted derivatives is well known. The molecules SbX3 are good acceptor and a wide range of neutral complexes have been prepared but it seems antimony trichloride is a weak acceptor as compared to antimony pentachloride. The halide complexes are more interesting because of the part played by the lone pair in determining the stereochemistry where 1:1 complexes have trigonal bipyramidal and 1:2 complexes have square pyramidal configurations. Complexes of antimony trichloride with aromatic hydrocarbon are also known but the presence of organic group in a molecule reduces its capacity to form complexes.DOI: http://dx.doi.org/10.3126/av.v4i0.12357Academic Voices Vol.4 2014: 45-48

1988 ◽  
Vol 43 (9) ◽  
pp. 1119-1124 ◽  
Author(s):  
Christina Ergezinger ◽  
Frank Weller ◽  
Kurt Dehnicke

Abstract N,N,N'-Tris(trimethylsilyl)benzamidine, [C6H5-C(NSiMe3)N(SiMe3)2], reacts with antimony trichloride in CH2Cl2 solution to form monomeric dichloroantimony-N,N'-bis(trimethylsilyl)- benzamidine, [SbCl2(NSiMe3)2C-C6H5]. Both benzamidine derivatives have been character­ized by crystal structure determinations. [C6H5-C(NSiMe3)N(SiMe3)2]: space group P21/c, Z = 4, 2278 observed independent refle­xions, R = 0,038. Lattice dimensions (19 °C): a = 1521,0(1); b = 656.7(1); c = 2163,0(1) β = 94,21(1)°. The compound forms monomeric molecules with CN distances of 126,6 pm, and 141,0 pm, respectively, corresponding to C=N̄-SiMe3 and C-N(SiMe3)2 moieties. [SbCl2(NSiMe3)2C-C6H5]: space group P21/c, Z = 4, 2707 observed independent reflexions, R = 0,027. Lattice dimensions (19 °C): a = 1212,7(1); b = 962,1(1); c = 1728,9(1) pm; β = 98,02(1)°. The compound forms monomeric molecules in which the antimony atom is surrounded by two chlorine atoms, and by the N atoms of the benzamidine chelate, forming a distorted trigonal bipyramidal arrangement, which is a consequence of the steric effect of the lone pair on the Sb atom.


1978 ◽  
Vol 33 (12) ◽  
pp. 1393-1397 ◽  
Author(s):  
R. D. Fischer ◽  
E. Klähne ◽  
J. Kopf

Abstract The first two examples of a novel series of organo-actinide complexes, [Cp3UXL] (Cp = η5 -C5H5, X = halide or pseudohalide anion, L = uncharged Lewis base), are described. The X-ray structure analysis of the system with X = NCS and L = CH3CN confirms an almost linear alignment (H3)CCNUNCS along with the coplanarity of the three Cp ring normals. The remarkable Lewis acidity of certain Cp3UX-compounds appears to be essential for the formation of oligomeric species [Cp3UX]∞ as well as for specific reactions of monomeric CP3UX.


2015 ◽  
Vol 79 (1) ◽  
pp. 33-49 ◽  
Author(s):  
Andrew G. Christy

AbstractWhen crustal abundance (A, measured in atomic parts per million) of a chemical element is plotted vs. number of mineral species in which that element is an essential constituent (S), a significantly positive correlation is obtained, but with considerable scatter. Repeated exclusion of outliers at the 90% confidence level and re-fitting leads, after the sixth iteration, to a steady state in which 40 of the 70 elements initially considered define a trend with log S = 1.828 + 0.255 log a (r = 0.96), significantly steeper than the original. Three other methods for reducing the effect of outliers independently reproduce this steeper trend. The 'diversity index' D of an element is defined as the ratio of observed mineral species to those predicted from this trend. D separates elements into three groups. More than half of the elements (40 of 70) have D = 0.5–2.0. Apart from these 'typical' elements, a group of 15 elements (Sc, Cr, Ga, Br, Rb, In, Cs, La, Nd, Sm, Gd, Yb, Hf, Re and Th) form few species of their own due to being dispersed as minor solid solution constituents, and a hitherto unrecognized group of 15 elements are essential components in unusually large numbers of minerals. The anomalously diverse group consists of H, S, Cu, As, Se, Pd, Ag, Sb, Te, Pt, Au, Hg, Pb, Bi and U, with Te and Bi by far the most mineralogically diverse elements (D = 22 and 19, respectively). Possible causes and inhibitors of diversity are discussed, with reference to atomic size, electronegativity and Pearson softness, and particularly outer electronic configurations that result in distinctive stereochemistry. The principal factors encouraging mineral diversity are: (1) Particular outer electronic configurations that lead to a preference for unique coordination geometries, enhancing an element's ability to form distinctive chemical compounds and decreasing its ability to participate in solid solutions. This is particularly noteworthy for elements possessing geometrically flexible 'lone-pair cations' with an s2 outer electronic configuration. (2) Siderophilic or chalcophilic geochemical behaviour and intermediate electronegativity, allowing elements to form minerals that are not oxycompounds or halides. (3) Access to a wide range of oxidation states. The most diverse elements can occur as anions, native elements and in more than one cationic valence state.


1980 ◽  
Vol 58 (7) ◽  
pp. 686-693 ◽  
Author(s):  
John F. Harrod ◽  
Asha Pathak

The oxidation of 2,4,6-tritertbutylphenol and several other alkyl and halophenols by CrO2Cl2 and VOCl3 was studied. The products of CrO2Cl2 oxidation are mostly quinones and diphenoquinones, whilst those of VOCL3 oxidation also include major amounts of dealkylated phenols and C—C coupled dimers. The product distributions are interpreted in terms of a mechanism involving phenoxyl radicals, ligand transfer from metal to radical, and either phenoxonium ions or metallate esters where there is sufficient electron withdrawal from the organic group for it to exhibit carbenium ion properties. The differences in behaviour between CrO2Cl2, VOCl3, and CuCl2 are attributed to different balances between the oxidation potential and Lewis acidity of the metal complexes. It is concluded that CrO2Cl2 is not a good model for proposed ferryl intermediate in heme oxidase systems since it induces 1 → 3 rather than 1 → 2 halogen shifts and an NIH shift that is best explained by carbenium ion-like intermediates.


1978 ◽  
Vol 29 ◽  
pp. L203-L204 ◽  
Author(s):  
Ian Davies ◽  
William R. McWhinnie ◽  
Nigel S. Dance ◽  
Colin H.W. Jones

2021 ◽  
Author(s):  
◽  
Peter Chapple

<p>Early-late transition metal heterobimetallic complexes with direct metal to metal interactions are desirable synthetic targets due to the complementary reactivity of the two different metals present in these compounds. The electron-rich late transition metal (often Rh, Ir, Fe, or Mo), and electron-poor early transition metal create an ideal environment for heterolytic bond cleavage in what is often termed ‘cooperative reactivity’. This project aimed to synthesise a zirconium-germanium heterobimetallic complex based on a known heterobimetallic ligand scaffold; 1.   The synthesis of the desired heterobimetallic 1 was attempted using two different synthetic approaches. The first involved the investigating the reactivity between an unsaturated zirconium nitrogen bond (an imidozirconocene) and a germanium(II) source with a lone pair of electrons (known as a germylene). The second approach investigated the reactivity between an unsaturated germanium nitrogen bond (a germanimine) and a zirconium(II) source. In order to have the highest chance of success, a wide range of germanium and zirconium complexes were synthesised.  The novel germylenes include [Ge(NAPHTMS)] (NAPHTMS = [1,8-((CH3)3Si)N)2C10H6]) and [Ge(BIANMes)] (BIANMes = [((2,4,6-Me(C6H2)N)2)C12H6)]). These proved to be unreactive towards the imidozirconium species [Cp2Zr(NAr*)(THF)] and [Cp2Zr(NDipp)(THF)] (Ar* = (2,6-(C6H5)2CH)-4-(tBu)C6H2), Dipp = (2,6-((CH3)2CH)C6H3)) as well as other amidozirconocenes. However, within these studies, the mixed coordination germanium species [[Ge(NAPHTMS)Ge(Bu)(NAPHTMS)]-[Li(THF4)]+] and [[Ge(NAPHTMS)Ge(Me)(NAPHTMS)]-[Li(THF4)]+]were synthesised. Density functional theory (DFT) molecular orbital calculations were used to help explain the observed reactivity.  With regards to the second approach, routes to new germanimine complexes such as [(HMDS)2Ge(NMes)] ((HMDS) = ((CH3)3Si)2N), Mes = (2,4,6-CH3(C6H3))), were explored, and several methods for generating “Cp2Zr” were examined. Although these conditions proved unsuccessful for generating 1, the reaction between dialkyl zirconocene with azides to form novel zirconocene triazenido complexes was discovered and the sterics affecting the synthesis of new germanimine complexes was investigated.</p>


1955 ◽  
Vol 33 (5) ◽  
pp. 797-803 ◽  
Author(s):  
F. E. Murray ◽  
W. G. Schneider

The nature of the intermolecular force field of the nitriles is considered on the basis of the electron orbital structure and charge distribution of the nitrile group. The directional nature of the force field is due to a well-directed lone pair orbital on the N atom, which may be expected to exhibit strong donor properties, and two π-orbitals which may exhibit weak donor properties. Accordingly with good acceptor molecules such as chloroform and hydrogen chloride, simple 1:1 molecular addition compounds should occur. The existence of molecular complexes of this type was confirmed with the aid of binary freezing-point diagrams which were determined for aceto-, propio-, butyro-, and benzo-nitrile with chloroform and hydrogen chloride. The 1:1 association complex was absent, however, in the system acetonitrile–chloroform. This is accounted for by the stronger association occurring in acetonitrile itself, the nature of which is discussed. The structure of the 1:1 molecular complexes is considered. Additional molecular complexes with lower nitrile mole ratios are indicated in the freezing-point diagrams. Of particular interest are the well-defined compounds appearing in the nitrile – hydrogen chloride systems with the composition RCN•5HCl. The possibility that the π-orbitals of the nitrile group may function as donors in these compounds is discussed, and a tentative structure is suggested.


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