Solange M. S. V. Doidge-Harrison

Sulphur substituted organotin compounds. Part 9. Crystal and molecular structure and reactions of [(p-chlorophenylthio)methyl]tricyclohexylstannane

Abstract The crystal and molecular structure of [(p-chlorophenylthio)methyl]tricyclohexylstannane (II) has been determined. In the two independent molecules of monoclinic II there are slightly distorted tetrahedral geometries about tin with intramolecular SnS distances of 3.29(1) and 3.26(1) A. Compound II reacts with N-bromosuccinimide, I2, Pb(OAc)4 or CF3CO2H to give XCH2SC6H4Cl-p (X = Br, I, AcO or H) and the appropriate tricyclohexyltin species; II is less reactive than Cy3SnCH2SeC6H4Cl-p towards I2. Oxidative cleavage of II by m-ClC6H4CO·O·OH provides mainly CH3S(O)C6H4Cl-p. The absorption maximum for the charge transfer complex of II and (NC)2CC(CN)2 is reported.

C-stannylated carbohydrate derivatives. Part 3. 1,2 : 5,6-Di-O-isopropylidene-3-C-(organostannyl)methyl-α-D-allofuranose derivatives. Crystal and molecular structure of 3-C-(dibutyliodostannyl)methyl-1,2 : 5,6-di-O-isopropylidene-α-D-allofuranose

Reaction of R2R′SnCH2Li(R = R′= Me or Bu) with 1,2 : 5,6-di-O-isopropylidene-α-D-ribohexofuranos-3-ulose provides 1,2 : 5,6-di-O-isopropylidene-3-C-(R2R′Sn)methyl-α-D-allofuranose (5): the glucose isomer was not obtained. Despite a hydroxy group being in a β- position to tin in compound (5), no β-elimination products are obtained on reaction with CF3CO2H, reaction proceeding instead at the C(5)–C(6) protecting group. Cleavage of an alkyl–tin bond in (5) by iodine is aided by nucleophilic assistance of the β-hydroxy group. 1H N.m.r. spectra of (5; R = Me, R′= I) in CDCl3 indicate the formation of a four-membered chelate ring due to SnOH interaction. The crystal structure of (5; R = Bu, R′= I) was determined; there is a distorted trigonal bipyramidal arrangement about tin with I and O axial; Sn—O 2.68(2)A.

C-stannylated carbohydrate derivatives, part 5. 1,2:5,6-Di-O-isopropylidene-3-C-(organostannyl)- and -3-C-(phenylstannyl)methyl-α-D-allofuranose compounds. X-Ray crystal and molecular structure of 1,2:5,6-di-O-isopropylidene-3-C-(triphenylstannylmethyl)-α-D-allofuranose

The crystal structure and the solid state (13C and 119Sn) and solution (1H, 13C and 119Sn) NMR spectra of 1,2:5,6-di-O-isopropylidene-3-C-triphenylstannylmethyl-α-D-allofuranose (1; R = Ph) have been obtained. The structure of compound (1; R = Ph) is similar in both phases and contains a slightly distorted tetrahedral tin atom [C–Sn–C valency angles range from 103.8(3) to 114.9(5)°]. The poxygen atom at C(3) in compound (1; R = Ph) is 3.01(1)A distant from Sn and is ideally sited to take part in nucleophilic assistance during Ph–Sn bond-cleavage reactions. Reactions of compound (1; R = Ph) and 1,2:5,6-di-O-isopropyl idene-3-C-R3Sn-α-D-allofuranose with electrophiles (e.g., I2or CF3CO2H) are also reported.

Addition of sulphenyl halides and thiocyanates to alkenyl-metal compounds. Structures of [1-chloro-2-(4-methyl-2-nitrophenyl)ethyl]-triphenylstannane and [2-(2-nitrophenyl)-1-thiocyanatoethyl]triphenylstannane

Abstract The crystal and molecular structures of Ph 3 SnCHClCH 2 SC 6 H 3 NO 2 -2-Y-4 (II, Y  Me) and Ph 3 SnCH(SCN)CH 2 SC 6 H 4 NO 2 - o (III) have been determined. Compounds II and Ill are adducts of Ph 3 SnCHCH 2 and the appropriate sulphenyl chloride and thiocyanate. Both compounds are monomeric and contain slightly distorted tetrahedral tin atoms. The intra-molecular SnS(R) distances in II (Y  Me) and III are 3.67 and 3.58 A, respectively. The solid state conformations are staggered and have dihedral angles SnCCS of 56.6 and 57.4° in II (Y  Me) and III, respectively, and ClCCS in II and SCCS in III 176.0° and 174.1°, respectively. From 3 J (HH) and 3 J ( 119 Sn 1 H) values, the solid state conformation of II (Y  Me) is calculated to be populated in solution for approximately 1/3rd of the time at 25°C.

Synthesis and reactions of arylselenomethylstannyl compounds, R3SnCH2SeAr. Crystal and molecular structure of [(m-methoxyphenylseleno)methyl]triphenylstannane

Abstract The crystal and molecular structure of [(m-methoxyphenylseleno)methyl]triphenylstannane, Ph3SnCH2SeC6H4OMe-m (II), has been determined. Compound II contains a slightly distorted tetrahedral tin atom with an intramolecular SnSe distance of 3.319(2) A. Reactions of II and Cy3SnCH2SeC6H4nCl- p (III) (Cy=cyclohexyl) with various reagents have been studied; III reacts with Pb(OAc)4, N- bromosuccinimide (NBS), I2 or CF3CO2H to give XCH2SeC6H4Cl-p (X=AcO, Br, I or H). Compound II reacts at the PhSn bond with Cl2Pt(COD) (COD=cycloocta-1,5-diene), at the SnCH2(SeC6H4OMe- m) bond with NBS, and at both bonds with I2. Absorption maxima for charge-transfer complexes with (NO2CC(CN)2 were recorded.

(Aroxymethyl)triphenyltin compounds: Crystal and molecular structure of triphenyl(p-toloxymethyl)tin

Compounds, Ph3SnCH2OAr, are available from Ph3SnCH2I and NaOAr in EtOH. The crystal and molecular structure of Ph3SnCH2OC6H4Me-p (II) has been determined by X-ray crystallography. The molecule in the crystal contains a slightly distorted tetrahedral tin atom [C-Sn-C valency angles varying from 106.9(5) to 114.1(6)°] with an intramolecular Sn---O distance of 2.900(11) Å. NMR spectral data for (II) and for Ph3SnCH2OC6H3Br2-2,4 are reported.