Synthesis and spectroscopic characterization of diethyltin (IV) derivatives of dipeptides: Crystal and molecular structure of diethyltin glycyltrosinate

Dipeptide complexes of the diethyltin(IV) moiety, Et2SnL, have been synthesized, H2L being glycylglycine (H2GlyGly), glycylalanine (H2GlyAla), alanylalanine (H2AlaAla), glycylvaline (H2GlyVal), valylvaline (H2ValVal), glycylmethionine (H2GlyMet), glycyltyrosine (H2GlyTyr). The crystal and molecular structure of the complex Et2SnGlyTyr has been determined by singlecrystal X-ray diffraction. It consists of monomeric units, with the tin atom having a considerably distorted trigonal bipyramidal environment. The dipeptide acts as a tridentate ligand bonding the tin of the C2Sn fragment (equatorial carbon atoms) with the peptide nitrogen atom (equatorial) and axial (monodentate) carboxyl oxygen a…

Synthesis and spectroscopic characterization of R3SnIV derivatives ofN-acetyldipeptides

Triorganotin(IV) derivatives of N-acetyldipeptides R3SnAcDip; RMe, Et, n-Bu, n-Oct, Cy or Ph (HAcDipN-acetylglycylglycine and N-acetylglycylvaline; RMe, n-Bu, Cy, HAcDipN-acetylglycylalanine) were obtained by neutralization of R3SnOH and HAcDip. The complexes were studied by means of 119Sn Mossbauer, IR and 1H, 13C and 119Sn NMR spectroscopy. The CSnC bond angles have been inferred by rationalization of Mossbauer nuclear quadrupole splittings as well as from NMR coupling constants. Correlations of Mossbauer isomer shifts with partial atomic charges on tin atoms have been determined: Polymeric trigonal bipyramidal structures, with near-planar R3Sn units and axial carboxylate (unidentate) and…

ChemInform Abstract: Organoelement Derivatives of Steroids: Synthesis and Structural Characterization of Diorganotin Chloride Adducts of Hormones.

Abstract Ten new diorganotin dichloride adducts of hormones of the type R 2 SnCl 2 ·2L [where R = Me, Et, n-Bu, Oct and Ph; L = 4-androsten-17s-ol-3-one ( A ); 5-androsten-3s-ol-17-one ( B ); 4-androsten-17α- methyl-17s-ol-3-one ( C ) and 3,17-dihydroxy-5- pregnene-20-one ( D )] have been prepared and characterized at 297 K and 223 K. Spectroscopic measurements (IR; Raman; 1 H, 13 C, 119 Sn NMR) suggest the dissociation or fast ligand exchange in solution at 297 K. Hexa-coordinated adducts with bonding through carbonyl oxygen and trans -R groups in octahedral geometry are formulated at 223 K.

Synthesis and spectroscopic characterization of dimethyl-, di-n-butyl-, di-t-butyl-and diphenyl-tin(iv) derivatives of dipeptides: Crystal and molecular structure of di-n-butyltin(iv) glycylvalinate

The dipeptide complexes R2SnL listed below have been synthesized: (a) Me2SnL; H2L = glycylalanine (H2GlyAla), glycylvaline (H2GlyVal), glycylmethionine (H2GlyMet), glycyltryptophan (H2GlyTrp), glycyltyrosine (H2GlyTyr); (b) nBu2SnL; H2L = H2GlyAla, H2GlyVal; (c) nBu2SnL.H2O; H2L = glycylglycine (H2GlyGly), H2GlyAla; (d) tBu2SnL; H2L = H2GlyAla, H2GlyVal; (e) tBu2SnGlyGly. H2O; (f) Ph2SnL; H2L = H2GlyAla, H2GlyVal, H2GlyTyr, H2GlyTrp; (g) Ph2Sn(HGlyVal)2. The crystal and molecular structures of nBu2SnGl Val have been determined by single-crystal X-ray diffraction. The polyhedron around tin is a distorted trigonal bipyramid, analogous to that of Et2SnGlyTyr (see Vornefeld et al., Appl. Organo…

Organoelement derivatives of steroids: Synthesis and structural features of organosilicon, -tin and -lead derivatives of cholesterol and desoxycholic acid

Some organo-Main-Group-IV-element compounds of steroids of the type R3M(COL), R2Sn(COL)2 and (R3M)2(HDCA) (where R = Me or Ph; M = Si, Sn and Pb; HCOL = cholest-5-en-3β-ol; H3DCA = 3α, 12α-dihydroxy-5β-cholan-24-oic acid), have been synthesized. The structures of these compounds have been investigated by vibrational, mass, NMR (1H, 13C, 29Si, 119Sn and 207Pb) and 119Sn Mossbauer spectroscopy. For Me3Sn(COL) both in solution and in the solid state an associated structure with distorted trigonal bipyramidal geometry around tin and three-coordinated oxygen atoms is postulated. Discrete tetrahedral geometries are assigned to Ph3M(COL) complexes and to R2Sn(COL)2 complexes in solution. The latte…

Bis(triorganometal) and diorganometal 1,3-dithiolates (R3M)2(C6H3XS2) and R2M(C6H3XS2) (M = Sn, Pb; X= H, Cl)

Abstract Bis(triorganometal) and diorganometal 1,3-dithiolates (R3M)2(C6H3XS2) (C6H5XS2 1,3-dithiobenzene (for X = H) or 1,3-dithio-4-chlorobenzene (for X = Cl); M = Sn, X = Cl, R = CH3, C6H5; M = Pb, X = H, Cl, R = CH3, C2H5) and R2M(C6H3XS2) (R = CH3, C2H5, C6H5; M = Sn, X = Cl; M = Pb, X = H, Cl) have been prepared as the first organometal IVB derivatives of 1,3-dithiols, and investigated by vibrational, 1H NMR, and (in the case of organotin compounds) Mossbauer spectroscopy. The triorganometal derivatives are monomeric and the diorganometal derivatives dimeric in solution (37° C). For the latter a twelve-membered ring structure is proposed for both solution and the solid state.

The structure and dynamics of Cl-substituted tetraphenyl- and tetrabenzyl-tin(IV)

Abstract The crystal and molecular structure of (o-ClC6H4CH2)4Sn has been determined by X-ray crystallography. Tin is in a slightly distorted environment. The molecular dynamics of (p-ClC6H4)4Sn, (o-ClC6H4)4Sn and (o-ClC6H4CH2)4Sn have been investigated by variable temperature 119Sn Mossbauer spectroscopy (VTMS). A Debye-solid behaviour has been detected for (p-ClC6H4)4Sn, where, on the other hand, no influence by hydrogen–chlorine interaction on the magnitude of the dynamics data and functions seems to occur. For the o-Cl-substituted derivatives, a non-Debye-solid character could be advanced.

X-ray crystal structure and antimony-121 Mössbauer spectrum of catecholato bis(1,10-phenanthroline)antimony(III) tetraphenylborate

The crystal structure of the title compound was solved by means of X-ray diffraction at room temperature. The salt consists of a tetrahedral tetraphenylborate anion and a complex cation containing a catecholatoantimony(III) unit chelated by two 1,10-phenanthrolines. The three bidentate ligands are essentially arranged in one half of the Sb coordination sphere, leaving ample space to accomodate the lone pair of electrons. The Mossbauer parameters of the title compound and of the complex (C6H4O2)SbF·Phen were measured and their rationalization accomplished in the light of their respective molecular structures.

119Sn Mössbauer spectroscopic studies of the products of the reaction of triorganotin(IV) derivatives with 6-thiopurine

Abstract A structural study of the products of the reaction of R 3 Sn IV derivatives (R = Me, Bu n , Ph) with 6-thiopurine, 6-TPH 2 , and its sodium salt, 6-TPHNa, has been undertaken using Mossbauer spectroscopy and the point-charge model rationalization of the Mossbauer parameter nuclear quadrupole splitting. The synthetic reactions have been carried out at ca . 0 °C, 20 °C and 50 °C. The Mossbauer spectra of the complexes AlK 3 Sn(6-TPH) are consistent with the occurrence of two distinct tin(IV) sites in samples prepared at the lower temperature, while one only site appears by increasing the temperature of the reaction. Two tin sites constantly occur in the products of the reactions invo…

(2-Chlorobenzyl)tris(2-pyridinethiolato)tin(IV).

In the title compound, (2-chlorobenzyl)tris(pyridine-2-thiolato)-kappa(2)N,S;kappa2N,S;kappaS-tin(IV), [Sn(C7H6Cl)(C5H4NS)3], two of the three pyridine-2-thiolato ligands (SPy) are bidentate and one is monodentate. The bonding C atom of the 2-chlorobenzyl group, the S atom of the monodentate SPy and the S and N atoms of the two bidentate SPy ligands form a distorted octahedron around the Sn atom. The three S atoms and the N atom of one of the bidentate SPy ligands occupy the equatorial positions, while the N atom of the second bidentate SPy ligand and the C(CH2) atom are axial. The axial N-Sn-C angle of 157.9 (1) degree demonstrates the heavy distortion of the octahedron.

Stannacycloalkyl and stannepinyl derivatives of dipeptides

Stannacyclohexyl and stannacycloheptyl derivatives of dipeptides (CH2)nSnAA · xH2O (H2AA = H2GlyGly, with n = 5, x = 2 or n = 6, x = 1; H2AA = H2GlyAla, H2GlyVal, H2GlyMet, with n = 5, 6, x = 1) and stannepinyl glycylglycinate monohydrate have been obtained by the reaction of (CH2)nSnCl2 or stannepinyl dichloride with Na2AA. According to infrared and 119Sn Mossbauer data of the solid compounds, AA acts as a tridentate ONN ligand and tin has a trigonalbipyramidal environment. An analogous structure has been inferred from 1H, 13C, and 119Sn NMR data for the undissociated molecules in methanol solution.

Di- and Tri-organotin(IV) Complexes ofN-Acetyltriglycine andN-Benzoyltriglycine: Synthesis and Spectroscopic Characterization

Di- and tri-organotin(IV) derivatives of N-acetyltriglycine and N-benzoyltriglycine (HA) were obtained by refluxing equimolar mixtures of the ligand and the organotin(IV) oxide or hydroxide in methanol or acetone. According to the spectroscopic data, triorganotin(IV) derivatives adopt a trigonal-bipyramidal structure in which the planar R 3 Sn IV unit is bonded by a monodentate carboxylate group and a donor group, presumably the amide C=O. The reaction of HA with the appropriate diorganotin(IV) compounds gave both dicarboxylates R 2 SnA 2 , with six-coordinated tin, and dimeric tetra-organodistannoxanes {[R 2 SnA] 2 O}2, in which the tin atoms are essentially five-coordinated.

Complexes of organometallic compounds. XLIX. A Mössbauer-zeeman spectroscopic study of glycylglycinato-O,N,N(2−) diphenyltin(IV), and the point-charge model rationalization of the quadrupole splittings of some glycylglycinato-O,N,N(2−) diorganotin(IV) complexes

Organozin- und organobleiderivate von N-(2,4-dinitrophenyl)glycin

Abstract Organotin and organolead derivatives of N -(2,4-dinitrophenyl)glycine (HDNG), R 3 MDNG (M = Sn, Pb; R = CH 3 , C 6 H 5 ) and (C 6 H 5 ) 2 Pb(DNG) 2 , have been prepared from R 3 MOH or [(C 6 H 5 ) 2 PbO] n and HDNG, respectively. (CH 3 ) 3 PbDNG was also obtained from (CH 3 ) 3 PbBr and TlDNG. According to spectroscopic data R 3 M groups in R 3 MDNG are essentially planar and are bridged by bidentate carboxylate groups of DNG. NH does not coordinate to M. Penta-coordination is also indicated by Mossbauer data of R 3 SnDNG. Also for (C 6 H 5 ) 2 Pb(DNG) 2 a chain structure but with hexacoordination of Pb is proposed. The compounds are monomeric in solution.

Infrared, Mössbauer and lattice dynamics studies of (3-mercaptopropionato)bis(trimethyltin(IV))

Investigations on organotin, organolead, lead(IV), and lead(II) dithiolates

Abstract Bis(triorganometal) 1,2-dithiolates (R3M)2S2R′ [(HS)2R′ = C7H8S2 for toluene-dithiol-3,4 (H2TDT); M = Sn, Pb; R = Ph; or (HS)2R′ = C10H14S2 for 1,2-dimethyl-4,5-bis(mercaptomethyl)benzene (H2DBB); M = Sn, R = CH3, C6H5; M = Pb, R = C6H5], diorganometal 1,2-dithiolates R2MS2R′ [(HS)2R′ = C6H6S2 for 1,2-dimercaptobenzene (H2DMB); M = Pb, R = CH3, C2H5, C6H5; or (HS)2R′ = H2TDT; M = Sn, R = CH3, C6H5; M = Pb, R = C6H5; or (HS)2R′ = H2DBB; M = Sn, R = CH3, C6H5; M = Pb, R = CH3, C2H2, C6H5; or (HS)2R′ = C8H6N2S2 for 2,3-dimercaptoquinoxaline (H2QDT); M = Pb, R = C6H5] and some lead(IV) and lead(II) dithiolates Pb(S2R′)n [(HS)2R′ = H2DMB, n = 2; (HS)2R′ = H2TDT, n = 2; (HS)2R′ = H2DBB, …

Synthesis and spectroscopic characterization of dicyclohexyltin derivatives of dipeptides, andin vitro effects against MDA-MB 231 breast cancer cells: Crystal structures of dicyclohexyltin glycylglycinate and glycylalaninate

Dicyclohexyltin derivatives Cy2SnL (Cy = cyclohexyl) of the dipeptides H2L, glycylglycine, glycylalanine, alanylglycine, glycylvaline, glycylmethionine, glycylphenylalanine and glycyltyrosine, have been obtained by neutralization of Cy2SnO and H2L. The crystal structures of Cy2SnL (L = glycylglycinate, glycylalaninate) have been determined by single X-ray diffraction. Tin in each case has a distorted trigonal bipyramidal environment with the dipeptide acting as a tridentate NNO-ligand. From IR-data, and in some cases from 119Sn Mossbauer and 119Sn NMR data, analogous molecular structures are inferred for the other compounds Cy2SnL. Spectroscopic data indicate that the solid-state structures…

Mono-aryltin(IV) and mono-benzyltin(IV) complexes with pyridine-2-carboxylic acid and 8-hydroxyquinoline. X-ray structure of p-chloro-phenyl-tris(8-quinolinato)tin(IV)·2CHCl3

Abstract Complexes RSn(O2CPy)3·2H2O and RSn(Ox)3, (PyCOOH=pyridine-2-carboxylic acid, HOx=8-hydroxyquinoline, R=o- and p-Tolyl, o- and p-ClC6H4=o- and p-ClPh, o-ClC6H4CH2=o-ClBenzyl; besides, R=Ph in RSn(Ox)3) have been synthesized and characterized by elemental analysis and determination of molecular weights in CHCl3 solutions. The structure of p-ClPhSn(Ox)3·2CHCl3 has been determined by X-ray diffractometry. The 7-coordinated tin atom of the monomeric compound is in the center of a pentagonal bipyramid formed by (p-ClPh)C and O and N atoms of the chelating Ox− ligands. The latter type of structure would hold for all complexes according to 119Sn Mossbauer (including the determination of th…

A study of dimethyltin(IV)-L-cysteinate in aqueous solution

The in vivo activity of some R2Sn-L-cysteinate complexes (R = Me, Et, n-Bu) against murine P-388 leukaemia has been tested. Only the Et2Sn(IV) complex showed a marginal positive effect. Trigonal bipyramidal tin environments with two carbon (R) atoms and the sulfur atom in the equatorial plane and oxygen (carboxylate) and nitrogen (NH2) in apical positions have been proposed for the solid compexes (R = Me, Et, n-Bu, Ph) on the basis of experimental Mossbauer parameters and infrared (IR) data. Aqueous solutions of the Me2SnL-cysteinate have been studied by IR, 1H NMR and 119Sn Mossbauer spectroscopy (in frozen solution) at different pH values to identify the Me2Sn(IV) species present. At pH >…

Synthesis and characterization of diorganotin(IV) derivatives of 2-mercaptopyridine and crystal structure of diphenyl pyridine-2-thiolatochlorotin(IV)

Diorganotin(IV) derivatives of 2-mercaptopyridine (HSPy), R2Sn(SPy)2, R2SnCl(SPy) (R = Me, iPr, nBu, tBu, Cy, Ph) and Cy2SnBr(SPy), were obtained from R2SnX2 (X = Cl, Br) and NaSPy. Ph2SnCl(SPy) crystals, as determined by singlecrystal X–ray diffraction, are monoclinic in the space group P21/n. Tin forms with the bidentate SPy ligand a four–membered chelate ring with a short NSnS bite angle of 64.8(1)° leading to a heavily distorted trigonal–bipyramidal environment about tin. Apical Cl–Sn–N angle = 156.1(1)° equatorial C–Sn–C angle = 121.9(2)°. From 119Sn Mossbauer and IR data, analogous structures are inferred for the other solid compounds R2SnX(SPy), and distorted octahedral molecular str…

ChemInform Abstract: Synthesis and Characterization of Diorganotin(IV) Derivatives of 2- Mercaptopyridine and Crystal Structure of Diphenyl Pyridine-2- thiolatochlorotin(IV).

Diorganotin(IV) derivatives of 2-mercaptopyridine (HSPy), R2Sn(SPy)2, R2SnCl(SPy) (R = Me, iPr, nBu, tBu, Cy, Ph) and Cy2SnBr(SPy), were obtained from R2SnX2 (X = Cl, Br) and NaSPy. Ph2SnCl(SPy) crystals, as determined by singlecrystal X–ray diffraction, are monoclinic in the space group P21/n. Tin forms with the bidentate SPy ligand a four–membered chelate ring with a short NSnS bite angle of 64.8(1)° leading to a heavily distorted trigonal–bipyramidal environment about tin. Apical Cl–Sn–N angle = 156.1(1)° equatorial C–Sn–C angle = 121.9(2)°. From 119Sn Mossbauer and IR data, analogous structures are inferred for the other solid compounds R2SnX(SPy), and distorted octahedral molecular str…

A119Sn Mössbauer spectroscopic study on complexes of di-and tri-organotin(IV) moieties with 2-mercaptoethanesulfonates, in the solid state and in aqueous solution

The configuration of the bonding environment of tin in the complexes [R2Sn(SCH2CH2SO3)2]2− (R = Me, Ph) and [Me3Sn(SCH2CH2SO3)]− has been determined to be tetrahedral both in the solid state and in aqueous solution (for the methyl derivatives). The coordination number of tin increases to five in aqueous solutions for the Me2Sn(IV) complexes in Hepes buffer (N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid; at least in fivefold excess, at pH 7.4) due to coordination by the tertiary amino nitrogen atom. No effect is detected due to the surfactant 2-hydroxypropylcellulose concerning both coordination to tin and influence on the Mossbauer parameters. The stoichiometry of mixed complex format…

The interaction of S,N-coordinated dimethyltin(IV) derivatives with deoxyribonucleic acid: structure and dynamics by119Sn Mössbauer spectroscopy

Complexes Me2SnCl(SPy) and Me2SnCl(SPym) (HSPy = 2-mercaptopyridine; HSPym = 2-mercaptopyrimidine), from ethanol solutions, interact with aqueous calf-thymus DNA yielding condensed phases with probable Me2Sn(SPy,SPym) (DNA monomer) stoichiometries of 1:1; the condensation of DNA is inferred originated from electrostatic bonding between complex cations Me2Sn(SPy,SPym)+ and the phosphate oxygen of the phosphodiester groups. Octahedral-or trigonal-bipyramidal tin environments are inferred from the point-charge model treatment of the 119Sn Mossbauer parameter nuclear quadrupole splitting, considering the bonding by S and N, or only S donor atoms from the ligand, as well as possible coordination…

Studies on the antitumor activity of complexes of R2Sn(IV) with penicillamine enantiomers and with 3-thio-propanoic acid, and correlation with structural aspects

Abstract The activity of diorganotin(IV) derivatives, with SnS bonds, against murine leukemia P-388, has been investigated. The water-soluble penicillamine (PenH2) complexes, Me2Sn(D-Pen), Me2Sn(L-Pen), Me2Sn(D-PenH)2 and Me2Sn(L-PenH)2, are essentially inactive, and do not show any dependence of the antitumor activity from the configuration about the chiral centre. The complexes with 3-thiopropanoic acid (H2Tpr), R2Sn(Tpr), are active for REt and Ph, in line with the general behaviour of R2Sn(IV) derivatives. The nature of the organotins in the vehicle of administration is investigated by 119Sn Mossbauer spectroscopy. The structures of solid state polymers, occurring in suspensions, are …

Complexes of organometallic compounds

Abstract Novel complexes RClSntrid, where R is Me, Ph, n-Oct, and trid 2− are dianions of tridentate “planar” ligands with ONO and SNO donor atoms, were synthesized and investigated in the solid state by infrared and Mossbauer spectroscopy. Possible configurations are discussed; polymeric trigonal bipyramidal structures seem to occur, although five-coordinated monomers as well as octahedral dimers (via oxygen or sulfur bridges) are not excluded.

Semi-empirical MNDO study of the structure of some diorganotin (IV) glycylglycinates

The geometrical structures of some diorganotin glycylglycinates have been obtained using the MNDO semi-empirical method. A good agreement with the experimental diffractometric data was found.

Mono-organotin(IV) and tin(IV) derivatives of 2-mercaptopyridine and 2-mercaptopyrimidine: X-ray structures of methyl-tris(2-pyridinethiolato)tin(IV) and phenyl-tris(2-pyridinethiolato)tin(IV)�1.5CHCl3

Mono-organotin(IV) and tin(IV) derivatives of 2-mercaptopyridine (HSPy) and 2-mercaptopyrimidine (HSPym), RSnL 3 (R=Me, n-Bu, Ph; L=SPy, SPym; R=Bz=benzyl, o-CIBz, oClC 6 H 4 , p-ClC 6 H 4 , o-tolyl, p-tolyl; L=SPy), RSnCIL 2 (R=Me, n-Bu, Ph; L=SPy, SPym), RSnCI 2 L (R=Me, n-Bu; L=SPy, SPym) and SnCI 4-n L n (L=SPy, SPym; n=2,4) were obtained from RSnCI 3 or SnCI 4 and NaL or by neutralization (R=Ph,p-tolyl; L=SPy, SPym). RSnCIL 2 and RSnCI 2 L were better prepared by comproportionation of RSnCI 3 and RSnL 3 . MeSn(Spy) 3 and PhSn(SPy) 3 .1.5CHCI 3 crystals, as determined by single-crystal X-ray diffraction, are monoclinic. In the discrete monomeric RSn(SPy) 3 units, three bidentate SPy lig…

6-Thiopurine complexes of organotin(IV) moieties. Synthesis and structural characterization by infrared and Mössbauer spectroscopy

Abstract The novel complexes Me3Sn(6-TP−1) and Bun2Sn(6-TP−1)2, where 6-TP−1 is the mono-anion of 6-thiopurine, have been synthesized. The sites of stannylation of 6-TP have been inferred from the known directions of electrophilic substitution reactions of 6-TP itself. The compounds have been characterized by infrared and Mossbauer spectroscopy. A solid state polymeric structure has been proposed for Me3Sn(6-TP−1), where planar SnC3 skeletons are bridged by 6-TP−1 (thione tautomer) axially bound to Sn through N(3) and N(1) atoms. For Bun2Sn(6-TP−1)2, a molecular structure has been advanced, with the ‘aromatic’ ligand anions chelating Sn by S-N(7) atoms.

119Sn M�ssbauer studies of bis[cysteinato(1?)-S]- and bis[penicillaminato(1?)-S]-diorganotin(IV) species in the crystalline state and in frozen aqueous solution

The bonding and the configuration of the tin environment in the title compounds {R2Sn[SCH2CH(NH3+)COO−]2 and R2Sn[SC(CH3)2CH(NH3+)COO−]2, indicated in the following as R2Sn(cysH)2 and R2Sn(penH)2 respectively} has been investigated through the determination of the Mossbauer-Zeeman spectra of Ph2Sn(cysH)2 and Ph2Sn(penH)2 in the solid state, and through conventional Mossbauer spectroscopy of Me2Sn(penH)2 in the solid state as well as of Me2Sn(cysH)2 and Me2Sn(penH)2 in aqueous solution (frozen). The treatment of the data by the pointcharge model approach suggested the general occurrence of a tetrahedral C2SnS2 core. In aqueous Hepes buffer, a tertiary amino nitrogen atom has been observed to…

Organoelement derivatives of steroids: synthesis and structural characterization of diorganotin chloride adducts of hormones

Abstract Ten new diorganotin dichloride adducts of hormones of the type R 2 SnCl 2 ·2L [where R = Me, Et, n-Bu, Oct and Ph; L = 4-androsten-17s-ol-3-one ( A ); 5-androsten-3s-ol-17-one ( B ); 4-androsten-17α- methyl-17s-ol-3-one ( C ) and 3,17-dihydroxy-5- pregnene-20-one ( D )] have been prepared and characterized at 297 K and 223 K. Spectroscopic measurements (IR; Raman; 1 H, 13 C, 119 Sn NMR) suggest the dissociation or fast ligand exchange in solution at 297 K. Hexa-coordinated adducts with bonding through carbonyl oxygen and trans -R groups in octahedral geometry are formulated at 223 K.

Diorganotin(IV)-2-mercaptopyrimidine complexes

The complexes formed between the diorganotin(IV) moieties, R 2 Sn(IV), and the ligand 2-mercaptopyrimidine, (H)SPym, were investigated. Complexes R 2 SnHal(SPym) and R 2 Sn(SPym) 2 [R = Me, i Pr, n Bu, i Bu, t Bu, cyclohexyl(Cy), Ph] were synthesized, and characterized by elemental analysis. In the solid state, chelation of SPym through S and N donors was established by IR spectroscopy, and the nature of the environment of tin centers was investigated by 119 Sn Mossbauer spectroscopy. From the dynamics of 119 Sn nuclei determined by variable-temperature measurements on representative compounds [Me 2 SnCl(SPym) and Cy 2- SnBr(SPym)], as well as by point-charge model treatment of nuclear quad…