Rajnish K. Sharma

Triorganoantimony(V) complexes with internally functionallized oximes: synthetic, spectroscopic and structural aspects of [R3Sb(Br)L], [R3Sb(OH)L] and [R3SbL2], crystal and molecular structures of [Me3Sb{ONC(Me)C4H3O}2], [Me3Sb{ONC(Me)C4H3S}2], 2-OC4H3C(Me)NOH and 2-SC4H3C(Me)NOH

Triorganoantimony(V) complexes with internally functionallized oximes of the type [R3Sb{ON=C(Me)Ar}2] (1) [R=Me, Pri; Ar=C5H4N, C4H3S, C4H3O] have been prepared by the reaction of R3SbBr2 with the corresponding oximes in 1:2 molar ratio in anhydrous benzene. Treatment of 1 with one equivalent of R3SbX2 afforded a redistribution product [R3Sb(X){ON=C(Me)Ar}] (2) [X=(a):Br, (b):OH]. The species, R3Sb(OH)L, may also be obtained by the controlled hydrolysis of 1 (R=Pri; Ar=C5H4N). All of these complexes have been characterized by elemental analyses, and IR and NMR (1H and 13C) spectroscopic studies. Crystal structures of [Me3Sb{ON=C(Me)C4H3O-2}2] (3), [Me3Sb{ON=C(Me)C4H3S-2}2] (4) 2-OC4H3C(Me)=NOH (5) and 2-SC4H3C(Me)=NOH (6) are reported. The geometry around the antimony atom in 3 and 4 is distorted trigonal bipyramidal with the carbon atoms of the SbMe3 unit in equatorial positions and the two oxygen atoms of the oxime group occupying axial positions (O(1)---Sb---O(2) 171.67(12) in 3 and 169.14(13) in 4). The free oxime is clearly hydrogen bonded (H---N 2.08 A in 6) to essentially form a dimer.

Synthesis, spectroscopic and structural aspects of some tetraorganodistannoxanes with internally functionalized oxime: crystal and molecular structures of [{R2Sn(ONC(Me)py)}2O]2 (R=Bun and Et) and 2-NC5H4C(Me)NOH

Diorganotin(IV) complexes of the type [{R2Sn(ON=C(Me)py)}(2)O](2)(R = Bu-n(1), Pr-n(2), Et (3) and Me (4)) have been synthesized by the condensation reaction of R2SnO with 2-NC5H4(Me)C=NOH (5) in 1:1 molar ratio in refluxing anhydrous benzene-toluene and characterized by elemental analyses and IR and NMR (H-1, C-13 and Sn-119) spectroscopy. Two sets of Sn-119 chemical shifts are observed in the Sn-119-NMR spectra of all of these compounds indicating the presence of two types of environment around the tin atoms in solution. The crystal structures of 1, 3 and 5 have been established by single crystal X-ray diffraction, The bonding in 1 differs from that in 3 but in both structures two different environments around the tin atoms are evident with the geometry around each tin atom being that of a distorted trigonal bipyramid with alkyl groups at the equatorial positions. The structure of 5 consists of chains of molecules arising from intermolecular hydrogen bonding involving the nitrogen atom of the ring.

Synthesis, spectroscopic and structural aspects of some tetraorganodistannoxanes with internally functionalized oxime. 2. Crystal and molecular structure of [{Me2Sn(ON=C(Me)C5H4N)}2O}]2·2[2-NC5H4(Me)C=NOH]

The title compound [{Me2Sn(ON=C(Me)C5H4N)}2O}]2·2[2-NC5H4(Me)C=NOH] was obtained during the reaction of Me2SnCl2 with the sodium salt of the ligand in 1:2 molar ratio in a refluxing methanol–benzene mixture. X-ray diffraction analysis of the compound reveals that it is the first tetraorganodistannoxane structural motif in which two molecules of free oxime are connected to the stannoxane framework and the two Sn---O distances of the four-membered planar Sn2O2 ring are identical.

SYNTHESIS AND CHARACTERIZATION OF 5- AND 6-COORDINATED MONOORGANOTIN(IV) COMPLEXES OF 2- AMINOCYCLOPENTENE-1-CARBODITHIOIC ACID AND ITS N-/S-ALKYL DERIVATIVE HAVING NS AND SS DONOR SYSTEM

Abstract Monoorganotin(IV) complexes of 2-aminocyclopentene-1-carbodithioic acid and its N-/S-alkyl derivatives of formula [equation] (where n= 1,2; R= -H, -CH3, -C2H5 and -nC4H9) and [equation] (where n = 1,2) have been synthesised by the reactions of butyltintrichloride with corresponding ligands in different stoichiometric ratios. The plausible structures of these derivatives have been proposed on the basis of physico-chemical and spectral (IR, 1H, 13C and 119Sn NMR) Studies.

ORGANIC DERIVATIVES OF ALKYLENE DITHIOPHOSPHATES. PART II: SYNTHESIS AND PROPERTIES OF 2- ACETANILIDE (BENZANILIDE) DERIVATIVES OF ALKYLENE DITHIOPHOSPHATES

Abstract Reactions of p- bromoacetanilide (benzanilide) with ammonium salt of alkylene dithiophosphates NH4 +; G =-CMe2CMe2-, -CH2CMe2CH2-, -CMe2CH2CHMe-, CH2CH2CHMe-) in 1:1 molar ratio in refluxing benzene solution yields; acetanilide (benzanilide) derivatives of alkylene dithiophosphates, OGOP(S)S C6H4NH COR (R = Me or Ph). The newly synthesized derivatives have been characterized by elemental analysis, molecular weight determination, IR, NMR (1H & 31P) spectral studies. In contrast to bidentate behavior in metal and organometal derivatives of alkylene dithiophosphate (adttp), the behavior of the dithiophosphato moiety in these derivatives is found to be monodentate. On the basis of above studies the formation of P(S)S-C linkage have been established.

Reactions of bis(N-phenylsalicylidene iminato)aluminium-di-μ-isopropoxo-di-isopropoxo aluminium(III) with glycols

Reactions of bis(N-phenylsalicylidene iminato)aluminium-di-μ-isopropoxo-di-isopropoxo aluminium(III), [C6H4O{CH=N(C6H5)}]2Al(μ-OPri)2Al(OPri)2 with glycols in 1:1 molar ratio in refluxing anhydrous benzene yielded binuclear complexes of the type, [C6H4O{CH=N(C6H5)}]2Al(μ-OPri)2Al(O-G-O) [where G = (CH2)2, CH2CH(CH3), CH2CH(C2H5), CH(CH3)CH(CH3), (CH2)5, C(CH3)2CH2CH(CH3), (CH2)6], respectively. All these binuclear complexes have been characterised by elemental analysis, molecular weight measurements and spectroscopic(IR and NMR) studies.

SYNTHESIS AND CHARACTERIZATION OF SOME MIXED LIGAND HETEROCYCLIC COMPOUNDS OF ALUMINIUM(III) CONTAINING ACETYLACETONE AND GLYCOL MOIETIES

The reaction of [Al(CH3COCHCOCH3)2(Opr-i)]2 with glycols (HO-G-OH) in 1:2 molar ratio in refluxing benzene yields H[(CH3COCHCOCH3)2 ][where G=G1=-C(CH3)2CH2CH(CH3)- or G2=-C(CH3)2C(CH3)2-]. These derivatives are soluble in benzene, chloroform and dimethyl sulfoxide and are monomeric in chloroform. Further reaction of H[(CH3COCHCOCH3)2 with alkali metal methoxide (MOCH3) in 1:1 molar ratio in methanol yields the bimetallic heterocyclic derivatives of the type [(CH3OH)M] [(CH3COCHCOCH3)2 ] (where M = Li, Na and K). Also these are soluble in methanol and dimethyl sulfoxide and are monomeric. These complexes show slight ionic character in 0.001M methanol solution. All derivatives have been characterized by elemental analyses, IR, 1H, 13C and 27Al NMR spectral studies. The 27Al NMR spectra show the presence of octahedrally coordinated aluminium atoms.

SYNTHESIS, CHARACTERIZATION AND STRUCTURAL ELUCIDATION OF TRIORGANOSILICON (IV) COMPLEXES OF 2-AMINOCYCLOPENTENE-1-CARBODITHIOIC ACID AND ITS N-/S-ALKYL DERIVATIVES

Abstract Reactions of chlorotrimethylsilane with sodium salts of 2-aminocyclopentene-1-carbodithioic acid and its N-/S-alkyl derivatives, having the general formula and in 1 : 1 molar ratio in refluxing benzene solution lead to the formation of triorganosilicon(IV) derivatives, and , respectively. Characterization of these complexes by elemental analysis, molecular weight measurements, and IR, NMR (1H, 13C and 29Si) spectral analysis reveals a four coordination around the silicon atom in trimethylsilicon(IV) derivatives of 2N-alkylaminocyclopentene-1-carbodithioic acid and five coordination in the S-alkyl 2-aminocyclopentene-1-carbodithioic acid derivative.

Molecular structure of bis(N-phenylsalicylideneiminato)aluminium-di(μ-isopropoxy)di(isopropoxo)aluminium(III) and its reactions with alkoxyalkanols

A novel heterocyclic derivative of aluminium(III) [C6H4O{CHN(C6H5)}]2Al(μ-OPri)2Al(OPri)21 has been synthesized by the reaction of aluminium isopropoxide with N-phenylsalicylidene imine in 1 ∶ 1 molar ratio in refluxing anhydrous benzene. Reactions of 1 with alkoxyalkanols in 1 ∶ 1 and 1 ∶ 2 molar ratios in refluxing anhydrous benzene yielded binuclear complexes of the types, [C6H4O{CHN(C6H5)}]2Al(μ-OPri)2Al(OCH2CH2OR)(OPri) and [C6H4O{CHN(C6H5)}]2Al(μ-OPri)2Al(OCH2CH2OR)2 (where RCH3, C2H5 and C4H9n), respectively. All of these binuclear complexes have been characterized by elemental analysis, molecular weight measurements, and spectral studies. The FAB mass spectrum and 27Al NMR spectrum of 1 indicate that it is a discrete unsymmetrical dimer containing four- and six-coordinated aluminium(III) atoms as confirmed by its single crystal X-ray structure.

Synthesis and Spectroscopic Characterization of Dibutylgermanium(IV) Complexes of 2-amino-cyclopentene-1-carbodithioic Acid and its N-/S-alkyl Derivatives

Abstract Dibutylgermanium(IV) complexes of the type (where R = H, CH3 C2H3 C4H9) and have been prepared by the reaction of dibutylgermanium(IV) dichloride with the sodium salts of N-/S-alkyl derivatives of 2-aminocyclopentene-l-carbodithioic acid in 1:2 molar ratio in benzene solution. All of these derivatives have been characterized by elemental analyses, spectroscopic (IR, 1H and 13C NMR) studies as well as by molecular weight determinations.