Synthesis and characterization of the coordination polymer [(THF)K(μ-OPri)2Al(μ-OPri)2]n

Reaction of [Al(OPri)3] with K(OPri), in 1:1 molar ratio in refluxing anhydrous tetrahydrofuran yields a polymeric complex [(THF)K(μ-OPri)2Al(μ-OPri)2]n. The complex is characterized by spectroscopic studies and single crystal X-raydiffraction analysis.

Fused thia-heterocycles via isothiocyanates. Part II. A convenient synthesis of some new thieno[2,3-b]thiopyran-4-one derivatives

A facile synthesis of some methyl 5-(arylamino)-4-oxothieno[2,3-b]thiopyran-6-carboxylates 6a–g is achieved via direct reaction of deprotonated methyl 3-(2,5-dichlorothien-3-yl)-3-oxopropanoate with aryl isothiocyanates in anhydrous tetrahydrofuran (THF) under reflux. Upon saponification of 6a,b, the ester group is eliminated, most logically via decarboxylation of the presumably-formed carboxyl group. Structures of the new compounds 6a–g and 7a,b are supported by microanalytical and spectral [NMR, MS electron impact (EI) and HRMS] data.

Mono-and Bis(cyclopentadienyl)hafnium(IV) Derivatives with Higher Fatty Acids

The reactions of Cp2HfCl2 with some higher monocarboxylic acids having straight chains, caprylic (C8H16O2), lauric (C12H24O2), myristic (C14H28O2), palmitic (C16H32O2), stearic (C18H36O2), and behenic (C22H44O2) acid, have been studied in anhydrous tetrahydrofuran in 1:1 and 1:2 molar ratios, respectively. The reaction products isolated, of types Cp2Hf(L)Cl, CpHf(L)2Cl (LH represents different carboxylic acids), have been characterised by conductivity and magnetic susceptibility measurements and spectral (infrared, electronic, 1HNMR and 13C NMR) data. The bonding of the carboxylato ligand in these complexes has been discussed and plausible structures have been established.

Ein- und Zweielektronen-Oxidation von Phosphor-Yliden mit Kupfer(II)-Salzen / One- and Twoelectron Oxidation of Phosphorus Ylides Using Copper(II) Salts

The reaction of CuCl2 with equimolar quantities of an ylide R3P=CH2 (1a-c, R=CH3, C2H5, C6H5) in anhydrous tetrahydrofuran at low temperature leads to oxidative coupling, with ethylidene-1,2-bis-phosphonium salts R3P⊕-CH2-CH2-P⊕R3 2X⊖ (2, 3a-c) as high- yield products. The process is interpreted as a one-electron transfer to give radical cations R3P⊕-ĊH2 (II) which subsequently undergo dimerization. The initial counterions CuCl2⊖ (in 2a-c) can be replaced by PF6⊖ (as in 3a-c). (C2H5)3P=CHCH3 (1d) yields the cation (C2H5)3P⊕-*CH(CH3)-*CH(CH3)P⊕(C2H5)3 with two chiral centers as a mixture of diasteromers RR/SS, RS. The ratio of the components is 2,8:1. as evaluated by NMR spectroscopy.The analogous reaction with (C6H5)3P=CHCH3 and (C6H5)3P=C(CH3)2 (1e, f) takes a very different course. Along with minor quantities of (C6H5)3P⊕CH2CH3/(C6H5)3P⊕CH(CH3)2 species, mainly 1-chloroalkyl-phosphonium cations are formed, which were again isolated as the hexafluorophosphates (4a, 4b: [(C6H5)3P⊕CH(CI)CH3]PF6⊕, [(C6H5)3P⊕C(Cl)(CH3)2]Pf6⊖). H-radical trapping from the medium by II ist proposed for the formation of the former, while a two- electron oxidation followed by addition of Cl⊖ is the most plausible mechanism for the generation of the latter

Complexes of Bis(cyclopentadienyl)titanium(III) chloride with some bidentate ligands

Bis(cyclopentadienyl)titanium(111) chloride (cp2TiCl) complexes with 1,l0-phenanthroline (phen), 2,2?-dipyridyl (dipy), o-phenylenediamine (phm), and α-picolylamine (picam) in anhydrous tetrahydrofuran to give cp2TiCl,1.5L where L is the bidentate ligand. In air-free water all showed the conductivity of 1 : 1 electrolytes, but were insoluble in the common organic solvents.