Thomas Gries

Synthesis and X-ray structure of [Ag2(Ph2X2)4][AsF6]2(X = S or Se); six-membered silver–sulphur and silver–selenium rings

The reaction of diphenyl disulphide with AgAsF6 in liquid SO2 leads to [Ag2(Ph2S2)4][AsF6]2- The X-ray structure [space group P, a= 10.902(4), b= 10.976(6), c= 13.308(7)A, α= 112.82(4), β= 92.43(3), γ= 107.69(3)°, Z= 1, and R= 0.041 for 5 139 unique observed reflections] shows a centrosymmetric six-membered ring, in which two silver atoms are connected by two bridging Ph2S2 ligands; further unidentate sulphur ligands complete irregular three-co-ordination at silver. The analogous reaction with diphenyl diselenide leads to the isostructural [Ag2(Ph2Se2)4][AsF6]2[space group P, a= 10.676(3), b= 11.253(3), c= 13.625(4)A, α= 66.40(2), β= 89.67(2), γ= 71.40(2)°, Z= 1, and R= 0.044 for 4 439 reflections].

Superacids Based on Pentafluoroorthotellurate Derivatives of Aluminum

The new Lewis acid Al(OTeF5 )3 and its acetonitrile adduct CH3 CN→Al(OTeF5 )3 were obtained by a simple one-step synthesis in batches of up to 15 g. Al(OTeF5 )3 and the adduct were characterized by vibrational spectroscopy (IR, Raman) and quantum-chemical calculations. Furthermore, five different salts of the new weakly coordinating anion [Al(OTeF5 )4 ]- were prepared in a two-step procedure. [Ph4 P][Al(OTeF5 )4 ], Cs[Al(OTeF5 )4 ], [Ph3 C][Al(OTeF5 )4 ], as well as the protonated benzene derivatives [C9 H13 ][Al(OTeF5 )4 ] and [C6 H7 ][Al(OTeF5 )4 ] were characterized by low-temperature single-crystal X-ray diffraction and NMR spectroscopy. Arenium salts have rarely been characterized in the solid state and were synthesized in this work in a simplified fashion.

Reaktionen von 1,2,4-Thiadiazol-3,5-dicarbonitril mit Schwefelchloriden: Röntgenstrukturanalyse von S3(CN)4Cl2·AsF5 und S3(CN)8Cl2/Reactions of 1,2,4-Thiadiazol-3,5-dicarbonitrile with Sulfur Chlorides: X-Ray Crystal Structure Analysis of S3(CN)4Cl2·A sF5 and S3(CN)8Cl2

The reactions between 1,2,4-thiadiazol-3,5-dicarbonitrile, S(CN)4, and sulfur chlorides (SCl2 and S2Cl2) in the presence of Adogen® 464 (Aldrich) proceeds with formation of S3(CN)4Cl2 (1) and S3(CN)8Cl2 (2). These main products were characterized by X-ray structure determination of an adduct 1a and of 2. This adduct 1a was obtained by addition of the Lewis acid AsF5 in liquid SO2. 1a crystallizes with one SO2 molecule in the space group P21/n with a = 1177.3(2), b = 1082.8(1), c = 1255.3(5) pm, β = 109.73(3)°, Z = 4, V = 1.5061 nm3. It contains two five-membered rings connected by a nitrogen atom. AsF5 is coordinated to one of the ring nitrogen atoms [N(1)] adjacent to the sulfur atom S(1) and C(1)Cl-group. The other ring contains an S(2)-S(3) bond of length 207.7(4) pm. The rings are planar within experimental error. 2 crystallizes in the space group P21/n with a = 782.12(6), b = 1498.1(5), c = 1217.8(2) pm, β = 102.43(1)°, Z = 4, V = 1.3934 nm3. 2 is formed by addition of one molecule of SCl2 to two molecules of S(CN)4.

Human Capital and International Capital Flows

In the traditional Heckscher-Ohlin type of trade and growth theory, capital mobility is not integrated. Embodied in products, factor mobility takes place by the way of commodity trade. As a consequence, H.-O. theory implies factor price equalization. Therefore, there are only few proposition to combine Heckscher-Ohlin trade theory and international factor mobility. The first approach is proposed in a model, which is frequently called the Kemp-Jones model [Ruffin (1984)]. The reason for capital mobility in this kind of model is a deviation in productivity. This recardian type of argument can not only imply trade, but also international mobility of capital. A second incentive for capital mobility was brought up by Fischer/Frenkel (1972). In the Fischer/Frenkel approach installation costs of capital induce capital mobility. Generally, capital mobility was discussed more as a problem of monetary macroeconomics than as component of pure trade theory. In the subsequent paragraphs a different view of integrating capital mobility into H.-O. trade theory is suggested [see also Gries (1993)]. Four characteristics modifying standard neoclassical open economy growth theory are important: The small open economy produces with three factors of production (labor, real capital and human capital). The production process described by the foreign exchange production function [see Findlay (1973,1984)]. Real capital and human capital are accumulated over time and labor is exogenously growing. A country’s economic fundamentals are characterized by the local immobile factor endowment [characteristic endowment] namely labor and human capital. Human capital is identified as the ’peoples skills’. Human capital is ’embodied’ in the population, and therefore is an immobile factor. Making use of results well known in labor economics, human capital and real capital are poor substitutes in the production process. In a survey on human capital Hamermesh (1986) finds: ”Perhapss the most consistent finding is that non production workers (presumable skilled labor) are less easily substitutable for physical capital than are production workers (unskilled labor). Indeed, a number of the studies find that nonproduction workers and physical capital are p- complements. This supports Rosens’ (1968) and Griliches (1969) results on capital- skill complementary hypothesis”(Hamermesh 1986, p. 461). The accumulation of human capital is determined by portfolio decisions and an intertemporal optimal program. Accumulated local human capital determines the local requirements of real capital. Real capital is supplied totally elastic on world markets and employed on a ’normal’ level of utilization. Real capital will never be the limiting factor for a potential momentary rise in production.