Synthese und Strukturbestimmung von (tBuP)4Sn(CH3)2 und (CH3)2Sn[(tBu)P?P(tBu)]2Sn(CH3)2

Synthesis and Structure Analysis of (tBuP)₄Sn(CH₃)₂ and (CH₃)₂Sn[(tBu)P? P(tBu)]₂Sn(CH₃)₂ The diphosphides K₂[(tBu)P? (tBuP)₂? P(tBu)] 7 or K₂[(tBu)P? P(tBu)] 8 react with (CH₃)₂SnCl₂ in a molar ratio of 1 : 1 to form the binary 5-membered ring system P₄Sn 4 a and the 6-membered ring system Sn(P₂)₂Sn 5 a respectively. When (CH₃)₂SnCl₂, however, is treated with 8 in a molar ratio of 2 : 1 the 4-membered ring system P₃Sn 2 a is formed which includes the fragmentation of the intermediate K₂[(CH₃)₂Sn ((tBu)P? P(tBu))₂] 9. 4 a and 5 a could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analyses; 2 a was identified only NMR spectroscopically.     

NMR investigations on Stannabicycloundecanes of the type RSn(CH2CH2CH2)3N

The ¹H, ¹³C, and ¹¹⁹Sn NMR data of seven stannabicycloundecanes of the type RSn(CH₂CH₂CH₂)₃N (1, R = Cl; 2 , R = Br; 3 , R = I; 4 , R = OH; 5 , R = SPh; 6 , R = Me; 7 , R = Sn(CH₂CH₂CH₂)₃N) are reported. From ¹H NMR coalescence data at low temperature the free activation enthalpies for the racemisation of the bicyclo[3.3.3]skeleton were estimated to be 37 ± 1 kJ/mol. They are independent of the substituent R. However, it decreases when the tin atom is replaced by silicon for R = Me.     

Experimental and ab initio structural study of the ketotin compounds,X3SnCR2CH2COMe: crystal structures of X3SnCMe2CH2COMe (X = Cl and I)

The MeCOCH₂CMe₂ ligand in X₃SnCMe₂CH₂COMe ( 2 ; X = halide) acts as a C,O‐chelating group both in the solid state and in non‐coordinating solutions. The intramolecular Sn? O bond lengths in trigonal bipyramidal 2 (X = Cl and I), as determined by X‐ray crystallography, indicate that the stronger interaction occurs in 2 X = Cl. Comparisons with the Sn? O bond lengths in the estertin trihalides, X₃SnCH₂CH₂CO₂R ( 1 ; R = Me), suggest that the latter form stronger chelates than do 2 . In chlorocarbon solution, 2 (X = Cl, I) undergoes exchange reactions, as shown by NMR spectra, to give all possible halide derivatives, ∑(Cl_nI_3?nSnCMe₂CH₂COMe) (n = 0–3). Various ab initio calculations on 2 and X₃SnCH₂CH₂COMe ( 3 ) have been carried out. Comparisons of the theoretical and experimental structures of 2 for X = Cl or I are reported. Copyright © 2005 John Wiley & Sons, Ltd.     

[{LiCH(CH2CH2OMen)SO2Ph}4] (OMen = Menthyl): Synthesis and First Structure of a Chiral Solvent Free Lithiated Sulfone with a Direct Li–C Bond

R*OCH₂CH₂CH₂SO₂Ph (R*OH = MenOH, (–)‐menthol, ( 3a ); BorOH, (1S)‐(–)‐borneol, ( 3b )) were found to react with n‐BuLi in n‐pentane/n‐hexane and toluene/n‐hexane under deprotonation yielding LiCH(CH₂CH₂OR*)SO₂Ph (R* = Men, ( 4a ); Bor, ( 4b )) which reacted with n‐Bu₃SnCl forming the requisite tri(n‐butyl)tin compounds n‐Bu₃SnCH(CH₂CH₂OR*)SO₂Ph (R* = Men, ( 5a ); Bor, ( 5b )) as diastereomeric mixtures. The identities of 5a and 5b were unambiguously proved by ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopic measurements. Solutions of 4a afforded crystals of [{LiCH(CH₂CH₂OMen)SO₂Ph}₄] ( 4a′ ) for which the structure was determined by single‐crystal X‐ray crystallography. Complex 4a′ crystallized in a tetrameric structure without any additional solvent molecules. There were found direct Li–C bonds (Li1–C1/Li2–C20 2.231(9)/2.236(9) Å). The tetrahedral donor set of Li is completed by three oxygen atoms. One oxygen atom comes from the OMen substituent via intramolecular coordination and two oxygen atoms come from SO₂ groups of neighboured LiCH(CH₂CH₂OMen)SO₂Ph moieties. Thus, a heterocubane structure with a Li₄S₄ core is built up.     

Transition-Metal-Substituted Gallanes: Synthesis and Spectroscopic Studies of Highly Polar σ(M—Ga) Bonds,Structures of trans-(Ph3P)(CO)3Co—Ga[(CH2)3N(C 2H5)2]R (R = Cl,CH3) and (n5-C5H5)(CO)2Fe—GaCl2 [N(CH3)3]

The salt elimination reaction of the transition carbonyl metal-lates [L(CO)_nM](Na/K) (M = Cr, Mo, W, Mn, Re, Fe, Co, Ni; L= CO, n⁵-C₅R₅, PR₃; n= 1-4; R= alkyl, aryl) with the base-stabilized galliumhalides Cl_aGaR₃ -a(Do) (R = H, alkyl, halide; Do = THF, N(CH₃)₃, NC₇H₁₃) or Cl_aGa[(CH₂)₃N-R₂](R)₂ - _a yielded almost quantitatively the transition metal-substituted, gallanes [L(CO)_nM]_aGaR₃ - _a(Do) and [L(CO)_n-M]_aGa[(CH₂)₃NR₂](R)₂ - _a, respectively. Residual halide functionalities in these complexes were selectively replaced by various other groups. The new compounds were characterized by means of elemental analysis, ¹H-, ¹³C-, ³¹P-NMR, MS, and lR v(CO) data. The single-crystal X-ray structure analysis of trans-(Ph₃P)(CO)₃Co-Ga[(CH₂) ₃N(C₂H₅)₂](R)( 6s : R = Cl, 6t : R= CH₃) showed s̀(Co-Ga) lengths of 237.78(4) and 249.5(1) pm, respectively. A short s̀(Fe-Ga) contact of 236.18(3) pm was found for (n⁵-C₅H₅)(CO)₂Fe-Ga-Cl₂[N(CH ₃)₃] ( 5a ). Low-pressure MOCVD experiments were performed to give thin films of analytically pure CoGa alloy.     

Zur Reaktion von cyclo‐Tristannazanen, [(CH3)2Sn–N(R)]3, mit den Trimethylderivaten des Aluminiums,Galliums und Indiums

The Reactions of cyclo ‐Tristannazanes, [(CH₃)₂Sn–N(R)]₃, with the Trimethyl Derivatives of Aluminium, Gallium, and Indium The cyclo‐tristannazanes [Me₂Sn–N(R)]₃ (with R = Me, ⁿPr, ⁱPr, ⁱBu) have been prepared from Me₂SnCl₂ and LiN(H)R in a 1 : 2 molar ratio. With MMe₃ (M = Al, Ga, In) they form the dimeric dimethylmetal trimethylstannyl(alkyl)amides [Me₂M–N(R)SnMe₃]₂ in good yields. The mass, NMR (¹H, ¹³C, ¹¹⁹Sn), and vibrational spectra are discussed and compared with the spectra of the tristannazanes. Thermolysis of the gallium amidocompounds splits SnMe₄ to form methylgallium imido derivatives with cage structures. The crystal structures of selected stannylamido complexes have been determined by X‐ray structure analysis.     

Synthese und Eigenschaften von Triphenylzinnmolybdaten mit kettenförmigen Anionen des Typs 1∞[(Ph3Sn)MoO4]–. Die Kristallstrukturen von (nPr4N)[(Ph3Sn)MoO4]·CH3CN, (nBu4N)[(Ph3Sn)MoO4], [Zn(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH und [Cu(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH

The reaction of Ph₃SnCl, (R₄N)₂[Mo₆O₁₉] and (R₄N)OH in a molar ratio of 6:1:10 leads to the formation of (R₄N)[(Ph₃Sn)MoO₄] (R = ⁿPr ( 1 ), ⁿBu ( 2 )). Compounds 1· CH₃CN and 2 have been charactarized by IR spectroscopy and single crystal X‐ray diffraction. 1· CH₃CN forms orthorhombic crystals, space group P2₁2₁2₁ with a = 1339.9(2), b = 1508.9(2), c = 1733.2(3) pm. 2 crystallizes in the monoclinic space group P2₁ with a = 1342.6(2), b = 2280.3(4), c = 1344.0(2) pm, β = 118.34(1). Both compounds 1 and 2 consist of isolated R₄N⁺ cations and polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains with an alternating arrangement of Ph₃Sn⁺ and MoO₄^2– groups. Treatment of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)copper(II) succinate yields [Cu(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 3 ). The zinc derivative [Zn(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 4 ) is obtained similarly by reaction of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)zinc(II) formiate. Compounds 3· 2DMF · EtOH and 4· 2DMF · EtOH crystallize in the monoclinic space group P2₁/n with a = 1998.0(2), b = 1313.3(1), c = 2181.6(2) pm, β = 90.97(1)° for 3 and a = 2015.4(1), b = 1316.7(1), c = 2157.0(1) pm, β = 90.40(1)° for 4 . Like in the cases of 1 and 2, polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains are observed. The [M(en)₂]²⁺ units (M = Cu, Zn) act as linkers between the $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains to give 2D layer structures with (6, 3) net topology.     

Die Kristallstruktur des Trimethylzinn-methansulfinats, (CH3)3Sn02SCH3

The Crystal Structure of Trimethyltin Methanesulfinate, (CH₃)₃SnO₂SCH₃ Trimethyltin methanesulfinate, (CH₃)₃SnO₂SCH₃ crystallizes orthorhombie in the space group A2₁22. The lattice constants are: a = 7.98 ± 0.01, b = 12.59 ± 0.02 and c = 17.83 ± 0.02 Å Within the crystal structure the Sn atoms are linked together via bridging RSO₂ groups to form a helical chain along [l00]. Each Sn atom is surrounded by three C and two 0 atoms in a trigonal bipyramidal arrangement. The Sn? C distances are in the range from 2.09 to 2.18 Å the Sn? 0 distance amounts to 2.23 Å.     

Synthese und Struktur eines Pentaalkylchlorohexastibans Sb6R5Cl [R = (Me3Si)2CH]

Synthesis and Structure of Pentaalkylchlorohexastibane Sb₆R₅Cl [R = (Me₃Si)₂CH] The reaction of RSbCl₂ [R = (Me₃Si)₂CH] with Na‐K alloy in tetrahydrofuran gives besides the known rings Sb_nR_n (n = 3, 4), (Me₃Si)₂CH₂ and the pentaalkylchlorohexastibane Sb₆R₅Cl ( 1 ). 1 was characterized by spectroscopic methods (MS, ¹H‐, ¹³C‐NMR, X‐ray diffraction). The structure of 1 consists of a folded four membered antimony ring in the all‐trans configuration with three alkyl groups and one Sb(R)—Sb(R)Cl fragment as substituents.     

Synthese und Festkörperstruktur des Koordinationspolymers {Zn[Sn(CH2SMe)4]0.5Cl2}n

Synthesis and Solid State Structure of the Coordination Polymer {Zn[Sn(CH₂SMe)₄]_0.5Cl₂}_n The tin compounds Sn(CH₂SMe)₄ and Sn(CH₂PPh₂)₄ are accessible from reaction of SnCl₄ with LiCH₂SMe and LiCH₂PPh₂, respectively. X‐ray quality crystals of Sn(CH₂PPh₂)₄ (tetragonal, ) are obtained from a benzene solution at 4 °C. The lithium methanide [Li(PMDTA)CH₂PPh₂], which was a starting material in the synthesis of Sn(CH₂PPh₂)₄ crystallized from a mixture of diethyl ether and pentane at ?20 °C in the monoclinic space group P2₁/c. The coordination polymer {Zn[Sn(CH₂SMe)₄]_0.5Cl₂}_n was synthesized from Sn(CH₂SMe)₄ and ZnCl₂ in benzene. The solid state structure of this coordination polymer reveals that {Zn[Sn(CH₂SMe)₄]_0.5Cl₂}_n possesses an infinite [Zn‐SMe‐CH₂‐Sn‐CH₂‐SMe‐]‐chain as its backbone (monoclinic P2₁/c).     

Transients from a mixture of [(R(O)Sn)2C(CH3)2]2 and (RCl2Sn)2C(CH3)2 [R = (SiMe3)2CH]: an identification in situ by 1D 119Sn and 2D 1H?119Sn HMQC NMR spectroscopy and electrospray mass spectrometry

The reaction of the 2,2‐bis(organodichlorostannyl)propane [(Me₃Si)₂CH(Cl₂)Sn]₂CMe₂ (A) with the corresponding organotin oxide {[(Me₃Si)₂CH(O)Sn]₂CMe₂}₂ (B) does not provide the corresponding normally expected tetraorganodistannoxane {[(Me₃Si)₂CH(Cl)SnCMe₂Sn(Cl)CH(SiMe₃)₂]O}_n but a complex reaction mixture. One major product, namely the 2,4,6,8‐tetraorgano‐2,6‐dichloro‐1,5,9‐trioxa‐2,4,6,8‐tetrastannabicyclo[3.3.1]nonane derivative [(Me₃Si)₂CHSnCMe₂Sn(Cl)CH(SiMe₃)₂]₂O₃ (C) was identified in situ by 2D ¹H? ¹¹⁹Sn and ¹H? ¹³C heteronuclear multiple quantum coherence and heteronuclear multiple bond correlation NMR spectroscopy as well as electrospray mass spectrometry. Compound C is proposed to be in equilibrium with an ionic species C′, the cation of which has an adamantane‐type structure. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis of sulphonated aminomethylphosphines and some nickel(II), palladium(II), platinum(II) and rhodium(I) complexes. Crystal structure of [Et3NH][(Ph2PCH2)2 N(CH2)2SO3]

Summary Aminoalkanesulphonic acids H₂N(CH₂) _n SO₃H, (n = 1, 2 or 3) react with phosphonium salts [R₂P(CH₂OH)₂]Cl (R = Ph or Cy, Cy = cyclohexyl) in the presence of Et₃N to give the sulphonated aminomethylphosphines [Et₃NH] [(R₂PCH₂)₂N(CH₂) _n SO₃] (R = Ph, n = 1, 2 or 3; R = Cy, n = 1). The single crystal X-ray structure of [Et₃NH] [(Ph₂PCH₂)₂N(CH₂)₂SO₃] has been determined. Some Ni^II, Pd^II, Pt^II and Rh^I complexes of the phosphines have been prepared.     

Synthese und Kristallstruktur des heterobimetallischen Diorganozinndichlorids (FcN,N)2SnCl2 (FcN,N—: (η5‐C5H5)Fe{(η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}—)

Synthesis and Crystal Structure of the Heterobimetallic Diorganotindichloride (FcN, N)₂SnCl₂ (FcN, N^—: (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2}^—) The heterobimetallic title compound [(FcN, N)₂SnCl₂] ( 1 ) was obtained by the reaction of [LiFcN, N] with SnCl₄ in the molar ratio 1:1 in diethylether as a solvent. The two FcN, N^— ligands in 1 are bound to Sn through a C‐Sn σ‐bond; the amino N atoms of the side‐chain in FcN, N^— remain uncoordinated. The crystals contain monomeric molecules with a pseudo‐tetrahedral coordination at the Sn atom: Space group P2₁/c; Z = 4, lattice dimensions at —90 °C: a = 9.6425(2), b = 21.7974(6), c = 18.4365(4) Å, β = 100.809(2)°, R1_obs· = 0.051, wR2_obs· = 0.136.     

Synthesis and spectral studies of diorganotin heterocyclic dithiocarbamate complexes and crystal structures of (2‐F‐Bz)2Sn(Cl) S2CN(CH2CH2)2NEt and (3‐Cl‐Bz)2Sn [S2CN(CH2CH2)2NEt]2 ⋅ 0.5HN(CH2CH2)2NH

Some new diorganotin(IV) complexes of heterocyclic dithiocarbamate having general formula R₂Sn(Cl)S₂CNR'₂ and R₂Sn(S₂CNR'₂)₂ [R = 2‐F‐Bz, 3‐Cl‐Bz; NR'₂ = N(CH₂CH₂)₂NMe, N(CH₂CH₂)₂NEt, and N(CH₂CH₂)₂NBz] have been prepared, respectively. Elemental analyses, IR, and NMR spectral data characterized all compounds. The crystal structures of (2‐F‐Bz)₂Sn(Cl)S₂CN(CH₂CH₂)₂NEt 2 and (3‐Cl‐Bz)₂Sn[S₂CN(CH₂CH₂)₂NEt]₂ ⋅ 0.5 HN(CH₂CH₂)₂NH 5 were determined by single crystal X‐ray diffractometer. In the crystal of complex 2 , the tin atom is rendered five‐coordination in a trigonal bipyramidal configuration by coordinating with S atoms of dithiocarbamate groups. For complex 5 , the central Sn atom exists in a skew‐trapezoidal planar geometry defined by two asymmetrically coordinated dithiocarbamate ligands and two 3‐chlorobenzyl groups. © 2005 Wiley Periodicals, Inc. 16:271–277, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20096     

The synthesis,NMR (1H, 13C, 119Sn) and IR spectral studies of some di‐ and tri‐organotin(IV) sulfonates: X‐ray crystal structure of [(n‐C4H9)2Sn(OSO2C6H4CH3‐4)2·2H2O]

A number of alkyltin(IV) paratoluenesulfonates, R_nSn(OSO₂C₆H₄CH₃‐4)_4?n (n = 2, 3; R = C₂H₅, n‐C₃H₇, n‐C₄H₉), have been prepared and IR spectra and solution NMR (¹H, ¹³C, ¹¹⁹Sn) are reported for these compounds, including (n‐C₄H₉)₂Sn(OSO₂X)₂ (X = CH₃ and CF₃), the NMR spectra of which have not been reported previously. From the chemical shift δ(¹¹⁹Sn) and the coupling constants ¹J(¹³C, ¹¹⁹Sn) and ²J(¹H, ¹¹⁹Sn), the coordination of the tin atom and the geometry of its coordination sphere in solutions of these compounds is suggested. IR spectra of the compounds are very similar to that observed for the paratoluenesulfonate anion in its sodium salt. The studies indicate that diorganotin(IV) paratoluenesulfonates, and the previously reported compounds (n‐C₄H₉)₂Sn(OSO₂X)₂ (X = CH₃ and CF₃), contain bridging SO₃X groups that yield polymeric structures with hexacoordination around tin and contain non‐linear C? Sn? C bonds. In triorganotin(IV) sulfonates, pentacoordination for tin with a planar SnC₃ skeleton and bidentate bridging paratoluenesulfonate anionic groups are suggested by IR and NMR spectral studies. The X‐ray structure shows [(n‐C₄H₉)₂Sn(OSO₂C₆H₄CH₃‐4)₂·2H₂O] to be monomeric containing six‐coordinate tin and crystallizes from methanol–chloroform in monoclinic space group C2/c. The Sn? O (paratoluenesulfonate) bond distance (2.26(2) Å) is indicative of a relatively high degree of ionic character in the metal–anion bonds. Copyright © 2003 John Wiley & Sons, Ltd.     

Multinuclear NMR spectra of (CH3)3SnCH2M(CH3)3 (MSn,Ge, Si,C) and some halogenated derivatives

Chemical shift and scalar coupling constant information has been obtained from the ¹H, ¹³C, ²⁹Si and ¹¹⁹Sn NMR spectra of a series of compounds (CH₃)₃SnCH₂M(CH₃)₃, where M = Sn, Ge, Si or C and with one or two CH₃? (Sn) groups replaced by Cl, Br or I. The (CH₃)₃M and (CH₃)₃MCH₂ groups appear to have opposite substituent effects on chemical shifts.     

Synthesis and Structures of Homoleptic Methyl‐ and Phenylthiomethylaluminium Complexes [Al(CH2SR)3](R = Me,Ph)

Sulfur‐substituted methylmercury compounds [Hg(CH₂SR)₂]( 1a, R = Me; 1b, R = Ph ) react with aluminium amalgam in refluxing toluene with transmetallation to give homoleptic tris(thiomethyl)aluminium complexes [Al(CH₂SR)₃]( 2a, R = Me; 2b, R = Ph ) (degree of conversion: >80%, isolated yields: 2a 63%, 2b 41%). Their identities were confirmed by NMR spectros‐copy (¹H, ¹³C) and X‐ray crystal structure analyses. In crystals of compound 2a the aluminium atoms possess a trigonal‐bipyramidal arrangement with the coordination polyhedron defined by three carbon and two sulfur atoms. Two of the three CH₂SMe ligands are bridging ligands (μ‐η²; 1kC:2kS), the third one is terminal bound (η¹; kC). The structure is polymeric. Crystals are threaded by helical chains built up of six‐membered Al₂C₂S₂ rings. Crystals of 2b are built up of centrosymmetrical dimers with six‐membered Al₂C₂S₂ rings having bridging CH₂SPh ligands (μ‐η²; 1kC:2kS). On each Al atom two terminal (η¹; kC)CH₂SPh ligands are bound. They exhibit quite different Al‐C‐S angles (116.7(4) and 106.5(3)?). Similar values (114.32115.7? and 109.52109.9?) were found in ab initio calculations of model compounds [{Al(CH₂SR)₃}₂]( 3a, R=H; 3b, R=Me; 3c, R=CH=CH₂ ). A conformational energy diagram for rotation of one of the terminal CH₂SH ligand in the parent compound 3a around the Al‐C bond is discussed in terms of repulsive interactions of lone electron pairs of sulfur atoms.     

Thermally Stable Heterobinuclear Bivalent Group 14 Metal Complexes Ar2M−Sn[1,8-(NR)2C10H6] (M=Ge,Sn; Ar=2,6-(Me2N)2C6H3; R=CH2tBu)

The first thermally robust Ge ^II −Sn ^II compound 1 and the structurally characterized Sn^II-Sn^II analogue 2 , which maintain their structural integrity in solution, were obtained by treating MAr₂ (M=Ge, Sn; Ar=2,6-(Me₂N)₂C₆H₃) with Sn[1,8-(NR₂)₂C₁₀H₆] (R=CH₂tBu). On the basis of structural and spectroscopic data, the M−Sn bond is regarded as the interaction of a MAr₂ donor with an Sn[1,8-(NR₂)₂C₁₀H₆] acceptor.     

Synthese und Kristallstrukturen der silylierten Tris-Phosphanimine R?C(CH2PPh2NSiMe3)3 mit R  H und CH3

Synthesis and Crystal Structures of the Silylated λ⁵-Phosphazenes R? C(CH₂PPh₂NSiMe₃)₃ with R = H and CH₃ The title compounds are obtained by Staudinger reaction from the corresponding tripodal phosphanes R? C(CH₂PPh₂)₃ and trimethylsilylazide. Both complexes are characterized by their IR and NMR spectra and by crystal structure analyses. H? C(CH₂PPh₂NSiMe₃)₃ ( 1 ): Space group P2₁/c, Z = 4, structure determination with 7833 independent reflections, R = 0.055. Lattice dimensions at ?50°C: a = 1399.5, b = 2311.4, c = 1678.9 pm, β = 112.92°. CH₃? C(CH₂PPh₂NSiMe₃)₃ ( 2 ): Space group P1 , Z = 2, structure determination with 9251 independent reflections, R = 0.057. Lattice dimensions at ?50°C: a = 1276.5, b = 1386.9, c = 1790.2 pm; α = 85.55°, β = 69.39°, γ = 62.99°. 1 and 2 form monomeric molecules which are distinguished by their conformation.     

Zur Struktur und Reaktivität von stannylierten Propylaminen und -sulfiden. Kristall- und Molekülstruktur von Bis(3-dimethylchlorostannylpropyl)sulfid S(CH2CH2CH2SnMe2Cl)2

Structure and Reactivity of Stannylated Propyl Amines and Propyl Sulfides. Crystal and Molecular Structure of Bis(3-chlorodimethylstannylpropyl)sulfide S(CH₂CH₂CH₂SnMe₂Cl)₂ The synthesis and reactivity of stannylated propyl amines and propyl sulfides, respectively, E(CH₂CH₂CH₂SnMe₃)₂ ( 1 , E ? NMe; 2 E ? S) and N(CH₂CH₂CH₂SnMe₃)₃ 3 are reported. 1 and 3 react with dimethyl dichlorostannane under thermal cyclisation to 1,5-dimethyl-5-chloro-1aza-5-stannabicyclo[3.3.0^1,5]octane Me(Cl)Sn(CH₂CH₂CH₂)₂NMe 4 and 5-chloro-1-aza-5-stannatricyclo[3.3.3.0^1,5]-undecane ClSn(CH₂CH₂CH₂)₃N 5 , respectively. The reaction of 2 with dimethyl dichlorostannane leads to the formation of bis(3-chloro-dimethylstannylpropyl)sulfide S(CH₂CH₂CH₂SnMe₂Cl)₂ 6 , whereas the treatment of 2 with tin tetrachloride yields the bis(3-di-chloro-methylstannylpropyl)sulfide S(CH₂CH₂CH₂SnMeCl₂)₂ 7 . The ¹H, ¹³C, and ¹¹⁹Sn NMR data are discussed. 6 crystallizes in the ortho-rhombic space group Pna2₁ with the unit cell parameters a = 2275.0(1), b = 733.6(2), c = 1062.0(4) pm, V = 1.77273 nm³, Z = 4. The structure was refined to a final R value of 0.041. Both tin atoms adopt distorted trigonal bipyramidal configurations as a result of intramolecular interactions with the bridging sulphur. The sulphur and the chlorine atoms occupy the apical positions. The Sn? S distances amount to 309.7(4) and 311.8(4) pm.