The Catalytic Methods of Synthesis of the Phosphorus Esters with Tertiary Polyfluoroalkyl Groups

Abstract

The phosphorylation of tertiary alcohols can be performed only in some exceptional cases. We established, that phosphorylation of tertiary fluoroalkanols H(CF₂) _nCMe₂OH (I, n = 2,4) with aryl- and polyfluoroalkyl-phosphorodicnlor-idates or aryl- and alkylphosphonic dichlorides in the presence of metal of metal salt catalysts yields chloroan-hydrides (II) and (III). When benzyl phosphorochloridates (IV) are used as phosphorylating agents, either products of phosphorylation or products of alkylation are formed depending on the nature of the substituent in the aromatic ring.     

Ruthenium phosphine complexes as catalysts of alternating copolymerization of ethylene and carbon monoxide

The properties of the ruthenium (II) phosphine complexes [Ru(dppe)₂(OTs)₂] and [Ru{PhP(CH₂CH₂CH₂PPh₂)₂}(OTs)₂] as catalysts of alternating copolymerization of ethylene and carbon monoxide were studied. The catalytic activity of these complexes in the absence of cocatalysis is low, but it is substantially increased in the presence of trifluoroacetic acid or 1,4-benzoquinone. These compounds are the first ruthenium complexes which catalyze copolymerization of ethylene and CO. Translated fromAkademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1119–1121, June, 2000.     

Ruthenium bis(phosphinite) pincer complexes

Resorcinol-based ruthenium bis(phosphinite) complexes were synthesized. Complexes RuCl(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (9) and RuH(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (10) were obtained by cyclometallation of 1,3-(Bu^t ₂PO)₂C₆H₃ with RuCl₂(DMSO)₄ in 2-methoxyethanol in the presence of Hünig’s base. The interconversion of complexes 9 and 10 was studied. The addition of carbon monoxide to complexes 9 and 10 yielded 18e adducts, RuCl(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (11) and RuH(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (12), respectively. In the case of complex 9, this reaction is reversible. Reaction of complex 10 with trifluoroacetic acid resulted in complex Ru(CF₃COO)(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (13), which reacted with carbon monoxide to give complex Ru(CF₃COO)(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (14). Based on the IR spectral data, the TFA ligand in complexes 13 and 14 is bound in a bi- and monodentate fashion, respectively. The structure of compound 9 was determined by X-ray diffraction analysis.     

Formation of paramagnetic intermediates under the conditions of Brookhart-type catalyst activation and operation

The formation of two types of paramagnetic species in the catalytic system NiBr₂(DAB)/ MAO under real catalytic conditions was found. These are Ni^II are Ni^I complexes with the diimine ligand and complexes with the radical anion ligand in the coordination sphere. Under catalysis conditions, these forms are in equilibrium with each other, the equilibrium being shifted towards the radical anion form upon substrate addition.     

Synthesis and X‐ray study of cis and trans isomers of 6‐cyano‐2‐oxa‐10‐thia‐1‐phosphabicyclo[4.4.0]decane‐1‐oxide

Intramolecular cyclization of bis(3‐chloropropyl)‐diethoxythiophosphorylacetonitrile 7, taking place under distillation in vacuo, yields 6‐cyano‐2‐oxa‐10‐thia‐1‐phosphabicyclo[4.4.0]decane‐1‐oxide 10 as a mixture of cis and trans isomers in a 2.3:1 ratio. The isomers were separated chromatographically. For both isomers, single crystals with nonequivalent enantiomeric ratios were obtained under crystallization. The structures of both isomers of bicyclophostone 10 are confirmed by X‐ray study of single crystals. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:163–170, 2000     

Re(I) Complexes as Backbone Substituents and Cross-Linking Agents for Hybrid Luminescent Polysiloxanes and Silicone Rubbers

This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane-co-dimethylsiloxane) (N₃-PDMS) was synthesized for incorporation of azide function in polysiloxane chain. [Re(CO)₃(MeCN)(5-(4-ethynylphenyl)-2,2′-bipyridine)]OTf (Re1) luminescent complex was used to prepare a luminescent copolymer with N₃-PDMS (Re1-PDMS), while [Re(CO)₃Cl(5,5′-diethynyl-2,2′-bipyridine)] (Re2) was used as a luminescent cross-linking agent of N₃-PDMS to obtain luminescent silicone rubber (Re2-PDMS). The examination of photophysical properties of the hybrid polymer materials obtained show that emission profile of Re(I) moiety remains unchanged and metallocenter allows to control the creation of polysiloxane-based materials with specified properties.     

Electrophilic substitution reactions of ferracarborane 3-(η5-Cp)-4-SMe2-3,1,2-FeC2B9H10

Mercuration and bromination reactions of ferracarborane 3-(η⁵-Cp)-4-SMe₂-3,1,2-FeC₂B₉H₁₀ (1) were investigated. Mercuration of 1 under mild conditions (mercury trifluoroacetate in dichloromethane) results in 8-monosubstituted mercury derivative as the only reaction product. Depending on the reaction conditions, bromination of 1 results in 8-mono- or 7,8-disubstituted bromo derivatives. The structures of the monomercury and dibromo derivatives of 1 were established by X-ray analysis. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1609–1615, September, 2000.     

Synthesis of rhodacarborane halide complexes [(η-9-Me2S-7,8-C2B9H10)RhX2]2 (X=Cl, Br, or I)

The reactions of the complex (η-9-Me₂S-7,8-C₂B₉H₁₀)Rh(η-cod) (cod is 1,5-cyclo-octadiene) with HX acids (X=Cl, Br, or I) in acetone afforded rhodacarborane halide complexes [(η-9-Me₂S-7,8-C₂B₉H₁₀)RhX₂]₂, which are carborane analogs of cyclopentadienyl halide rhodium complexes [(η-C₅R₅)RhX₂]₂. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1817–1819, September, 1999.