Some new bimetallic carboxylates of tin and germanium with general formula where R1 = m-CH3C6H4, p-CH3C6H4, C6H5, R2 = o-CH3C6H4, p-CH3C6H4, o-CH3OC6H4, C6H5, CH3, have been prepared by the condensation reaction of diethyltin oxide and triarygermyl(substituted)propanoic acid in 1:2 mole ratio, respectively, and characterized by multinuclear (1H, 13C, 119Sn) NMR, 119mSn Mössbauer and IR spectroscopy. The X-ray crystal structure of the ligand I4 [(C6H5)3GeCH(o-CH3OC6H4)CH2COOH] delineate four coordinated germanium atom with a peculiarity of having a molecule of solvent (CHCl3). The chiral center in the synthesized compounds was identified on the basis of 1H NMR data and measurements of angle of rotations. 相似文献
Nickelacycles of the type [(py)2Ni(CH2CH2COO)] (1a), [(py)2Ni(C(Et)C(Et)-COO)] (2a), and [(py)Ni(CH2C(CH3)C(CH3)-CH2-COO)] (3a) were synthesized and structurally investigated by NMR, IR spectroscopy and in case of 1a and 2a by X-ray diffraction analysis. In 1a and 2a the Ni(II) ion has square-planar geometry, in contrast to the η3allyl compound [(bipy)Ni(CH2C(CH3)C(CH3)-CH2-COO)] (3b), in which nickel center adopts square-pyramidal geometry. 1a reacts with di(2-pyridyl)dimethylsilane (Me2(2-py)2Si) under exchange of the pyridine ligands to give 1c. 1a-3a and their bipy derivatives react with di-p-tolyldisulfide to form β-thioesters upon workup. Furthermore, reaction of 2-bromopropiophenone with nickelacycles of the type 2 results in the formation of 3,4-diethyl-6-hydroxy-5-methyl-6-phenyl-5,6-dihydro-2H-pyrane-2-one in good yields (64-75%). These reactions offer attractive new preparative routes for functionalized organic compounds. 相似文献
Diphenylphosphorous chloride and methyl iodide add readily to the N-bonded P(III)-atom of (C6H5)2P? P(C6H5)3?N? P(C6H5)2 forming the salts [(C6H5)2P? P(C6H5)2 N P(C6H5)2? P(C6H5)2]Cl and [(C6H5)2P? P(C6H5)2 N P(C6H5)2. CH3]I, respectively. A similar behaviour is observed with sulfur: Under mild conditions (C6H5)2P? P(C6H5)2?N? P(C6H5)2 = S is formed but forcing conditions are required to produce S = P(C6H5)2? P(C6H5)2?N? P(C6H5)2?S. The monosulfide is also obtained by treating (C6H5)2P(S)N[Si(CH3)3]2 with diphenylphosphorous chloride, indicating the favoured formation of the phosphazene system as compared with the phosphazane system Confirmation of the structures comes from 31P nmr and IR data, and for the sulfides also from their degradation with bromine. 相似文献
1,3-Cyclooctadiene reacts with trimethylaluminum and potassium according to the equation 4K + 4Al(CH3)3 + 2C8H12 3K[Al(CH3)4]+K[(C8H12)2Al] to give potassium bis(3,8-cis-cyclooctenyl) aluminate. The compound can be described as a bicyclo derivative of cyclooctene formed by the 1,4 addition to 1,3-cyclooctadiene. The structure of the complex was determined from 4500 unique data measured by single crystal X-ray diffractometer techniques. Full matrix least squares refinement gave final agreement factors of R1 = 0.043 (observed data) and R2 = 0.045 (all data) in the monoclinic space group P21/c (a = 9.658(6), b = 12.220(8) and c = 14.150(9)Å; β = 113.85(1)°; V = 1527.43 Å; Z = 4 for ?calc = 1.23 g cm?3). 相似文献
The reaction of the ansa-zirconocene meso-[C2H4(4,7-Me2Indenyl)2]ZrMe2 with B(C6F5)3 afforded, besides the expected ion pair with outward anion, also a minor isomer (molar fraction 0.043) with the bulky methylborate anion in the inward site. 2D 1H EXSY experiments revealed exchange between the two isomers, at T > 320 K, through the migration of the anion between outward and inward sites. The presence of free B(C6F5)3 fastened the exchange, suggesting B(C6F5)3 attack on the zirconium bound methyl ligand of the two ion pairs. 相似文献
