G. Srivastava

SYNTHESIS AND CHARACTERIZATION OF 2-MERCAPTO-2-THIONO-1,3,2-DIOXAPHOSPHOLANES AND DIOXAPHOSPHORINANES

Abstract 2-Mercapto-2-thiono-1,3,2-dioxaphospholanes and dioxaphosphorinanes, have been synthesized by the reactions of phosphorus pentasulphide with some 1,2-diols (viz., butane-2,3-diol and 2,3-dimethylbutane-2,3-diol) and 1,3-diols (viz., 2-methylpentane-2,4-diol, 2,2-dimethylpropane-1,3-diol and 2,2-diethylpropane-1,3-diol) in 1:2 molar ratio in dry benzene. These volatile compounds have been purified by distillation under reduced pressure. The 2-methylpentane-2,4-diol derivative, however, decomposed during attempted distillations. These new compounds have been characterized by elemental analysis, molecular weight determinations, measurement of pK a values and IR as well as NMR spectroscopic studies. The ammonium and sodium salts of some of these acids have also been characterized.

Synthesis and reactions of triorganotin dialkyldithiophosphates

Abstract Triorganotin dialkyldithiophosphates, (RO) 2 P(=S)SSnR′ 3 (R = Et, i-Pr, n-Pr or Ph and R′ = Me, Et, Bu or Ph), have been synthesised by the interactions of triorganotin hydroxides, oxides and chlorides with dialkyldithiophosphoric acids, (RO) 2 P(=S)SH, or their (Na, NH 4 or lead) salts in anhydrous benzene. An ester-type, structure is proposed, in which the diethyldithiophosphate moiety shows monodentate behaviour.

Tin-119, phosphorus-31, carbon-13 and proton nuclear magnetic resonance and Mössbauer studies of mono-, di- and tri-organotin(IV) dialkyldithiophosphates

Abstract 119 Sn, 31 P, 13 C and 1 H NMR chemical shifts of organotin(IV) dialkyldithiophosphates have been measured in CDCl 3 . The 119 Sn NMR chemical shifts and || 1 J ( 119 SnSn- 13 C)|| and || 2 J ( 119 Sn- 1 H)|| of triorganotin(IV) dialkyldithiophosphates are consistent with tetrahedral, four-coordinated tin, although Mossbauer studies indicate five-coordinated tin in the solid state. The 119 Sn NMR chemical shifts, || 2 J ( 119 Sn- 1 H)|| and Mossbauer parameters of mono- and di-organotin(IV) dialkyldithiophosphates are indicative of weak coordination of the ligands to tin.

Mixed halide dialkyldithiophosphate derivatives of arsenic(III) and antimony(III)

Abstract Mixed chloride dialkyldithiophosphates of arsenic(III) and antimony(III), [(RO) 2 PSS] n MCl 3−n (M = As, Sb; n = 1, 2; R = C 2 H 5 , n -C 3 H 7 , i -C 3 H 7 and i -C 4 H 9 ) have been synthesized for the first time by the reac metal chlorides with sodium dialkyldithiophosphates or alternatively by co-disproportionation reactions of metal chlorides with metal tris (dialkyldithiophosphates) in different stoichiometric ratios. Mixed halide dialkyl-dithiophosphates of antimony(III) have also been prepared by the cleavage reactions of antimony tris (diisopropyldithiophosphate) with bromine or iodine. Hydrolysis reactions of a few of these compounds have also been studied. The new compounds have been characterized by elemental analyses, molecular weight determinations (cryoscopic) as well as IR and NMR ( 1 H, 31 P) data; chelated structures with bidentate dialkyldithiophosphate groups are proposed.

Schiff base complexes of organotin(IV). Reactions of trialkyltin(IV) chlorides and alkoxides with N-substituted salicylideneimines

Eighteen new volatile N-substituted salicylideneiminatotrialkyltin derivatives have been synthesized by the reactions of trialkyltin chlorides or alkoxides with the corresponding Schiff bases. On the basis of infrared and proton magnetic resonance measurements, five coordination is proposed for tin in these complexes.

Triorganotin(IV) O,O-alkylene dithiophosphates

Abstract The O , O -alkylene dithisphosphates of triorganotin(IV) of the general formula R 3 SnS 2 PO 2 G (where R = C 6 H 5 , n-C 4 H 9 , n-C 3 H 7 , n-C 2 H 5 and CH 3 ; G = CH 2 C(CH 3 ) 2 CH 2 , C(CH 3 ) 2 C(CH 3 ) 2 and C(CH 3 ) 2 CHCH 3 have been synthesized by treatment of triorganotin(IV) chlorides with ammonium O , O -alklene dithiophosphates in 1/1 molar ratio in benzene. These novel complexes are either white crystalline solids or distillable liquids; all are soluble in common organic solvents are are monomeric in refluxing benzene. Like dialkyldithiophosphate derivatives of triorganotin(IV), these cyclic chain derivatives appear to be tetrahedral, the ligands behaving as unidentates.

Organic derivatives of tin V. Synthesis and reactions of alkyltin trialkoxides

Summary Alkyltin trialkoxides, RSn(OR′)3 (R = Et, n-Bu and R′= CH3, C2H5, i-C3H7, n-C4H9 and t-C4H9) have been synthesised from alkyltin trichlorides and the corresponding sodium alkoxide. Mixed derivatives of the type BuSnXn(OPr-i)3 (X = Cl, CH3CO2 and C2H5CO2) were obtained by exchange reactions. Reactions of butyltin triisopropoxide with protic reagents (e.g., H2O, (CH3)2C=NOH, o-HOC6H4OH, C6H5CH2NH2, NH2CH2CH2NH2, i-PrNHCOCH3, n-BuNHCOCH3, HCONH2 and CH3CONH2) have been studied. Dialkyltin acetamido derivatives have also been synthesised. IR and NMR spectra and molecular weights of the new products are reported and discussed.

Alkylenedithiophosphate derivatives of arsenic(III), antimony(III) and bismuth(III)

Abstract Tris(alkylenedithiophosphates) of arsenic(III), antimony(III) and bismuth(III), have been synthesized by the reactions of alkylenedithiophosphoric acids with metal oxides and chlorides and of their ammonium salts with metal chlorides in suitable solvents. Mixed chloride alkylenedithiophosphates of arsenic(III) and antimony(III), have been obtained by the reactions of metal chlorides with ammonium alkylenedithiophosphates at 1 : 1 and 1 : 2 molar ratios or alternatively by the co-disproportionations reactions of metal chlorides with metal tris(alkylenedithiophosphates) at different (2 : 1 and 1 : 2) molar ratios. These new compounds have been characterized by elemental analyses, molecular weight measurements and spectroscopic (IR, and 1H and 31P NMR) data. Chelated structures with bidentate alkylenedithiophosphate groups have been proposed for all these derivatives.

Diorganotin(IV) bis(O,O-alkylenedithiophosphates)

Abstract O,O-Alkylenedithiophosphates of diorganotin(IV) of the type R2Sn[SP(S)O2G]2 (R = Me, Et, n-Bu, Ph; G = CH2CMe2CH2, CMe2CMe2, CMe2CH2CHMe) have been synthesized by the reactions of diorganotin(IV) dichlorides with ammonium O,O-alkylenedithiophosphates or that of diorganotin(IV) oxides with O,O-alkylenedithiophosphoric acids in 1:2 molar ratio in benzene. These new complexes are white solids which are soluble in common organic solvents and are monomeric in refluxing benzene; and they have been characterized by elemental analysis and by different spectroscopic (IR, 1H, 13C, 31P and 119Sn NMR) studies, on the basis of which a six coordinated octahedral structure has been suggested in solution.

O,O′-dialkyl, diaryl and alkylene dithiophosphato derivatives of copper(II) and copper(I); adducts of copper(I) dithiophosphates with triphenyl phosphine: crystal and molecular structure of Cu[S2]·2P(C6H 5)3

Abstract Copper(II) bis(dithiophosphates), Cu[S2P(OR)2]2 (where R =CH2CH2CH3; C6H5) and Cu[S2POGO]2 [where G =C(CH3)2CH2CH(CH3),CH2C(CH3)2CH2, C(CH3)2C(CH3)2 and CH2CH2CH(CH3)−], were precipitated from aqueous solutions of CuSO4·5H2O and ammonium salts of dithiophosphoric acids and gave on treatment with CH3OH in CH2Cl2 solution the corresponding copper(I) derivatives, which form 1:2 adducts with triphenylphosphine. These compounds have been characterized by molecular weights, magnetic moments, IR, electronic, 1H and 31P NMR spectral measurements. Square planar geometry for the copper(II) complexes and tetrahedral geometry for the copper(I) complexes are suggested. The structure of a representative compound Cu[S2 POCH 2 C(CH 3 ) 2 CH 2 O ]·2P(C6H5)3 has been characterized by single crystal diffraction. Attachment of the dithiophosphato group to copper(I) is almost symmetrical with CuSav = 2.461 A and the overall geometry around the metal is distorted tetrahedral.