Sn Bridges Research Articles

Nonlinear Kinetic Inductance Sensor

The concept of nonlinear kinetic inductance sensor (NKIS) of electromagnetic radiation is proposed. The idea is based on divergency of kinetic inductanceLk∼dq/dI(ℏqis a momentum of superconducting electrons,Iis a supercurrent) of hybrid superconductor/normal metal (SN) bridge at currentI*Idep(Idepis a depairing current of the hybrid) and temperatureT* much smaller than critical temperatureTc. It makes possible to have large change of phase differenceδϕalong SN bridge in current biased regime atI≃I*even for small electron temperature increase. Appearance ofδϕis accompanied by the change of the current and magnetic flux through the coupled superconducting ring which could be measured with help of superconducting quantum interference device (SQUID). In some respect proposed sensor may be considered as a superconducting counterpart of transition edge sensor (TES) those work is based on large derivativedR/dT(Ris a resistance) nearTc. Because atI≃I*SN bridge is in gapless regime there is no low boundary for frequency of detected electromagnetic radiation. Our calculations show that such a sensor can operate in single photon regime and detect single photons with frequencyν≳10 GHz. We argue that the nontrivial dependenceI(q)of SN bridge could be also used in detectors of continuous electromagnetic radiation, current and magnetic field sensors.

Synthesis, structure and property of diorganotin complexes with chiral N-(5-chlorosalicylidene)valinate ligand

Six new diorganotin N-[(5-chloro-2-oxyphenyl)methylene]valinates, R2SnL (R = Me, 1; Et, 2; L = 5-Cl-2-OC6H3CH = NCH(i-Pr)COO: (S)-, a; (R)-, b; (RS)-, c), have been synthesized from the reaction of R2SnCl2 with the chiral ligand KHL (potassium salt of HL) in different solvents and characterized by elemental analysis, IR, NMR (1H, 13C and 119Sn) spectra. In benzene, the configuration of the chiral ligand was retained. (S)-Enantiomers (1a and 2a) and (R)-enantiomers (1b and 2b) display discrete molecular structures with distorted trigonal bipyramidal geometries in which two C atoms of organic groups (R) and the imino N atom occupy the equatorial positions and a phenoxide O and an unidentate carboxylate group O atom are in the axial orientation. In the methanol, the chiral ligand was racemized. 1c⋅MeOH is a centrosymmetric dimers formed by (R)- and (S)- enantiomers through two SnO⋅⋅⋅Sn bridges. The coordination geometry of the Sn atom can be described as a distorted pentagonal bipyramid with two methyl groups in axial positions. The crystal of 2c is composed of two threefold symmetric trimers, a [Et2SnL-(R)]3 and a [Et2SnL-(S)]3, with a macrocyclic 12-membered ring structure formed by the bidenate bridging coordination of carboxylate group to tin atoms. Each tin atom is six-coordinated in distorted [SnC2NO3] octahedron geometry. The fluorescence properties of ligand KHL and complexes 1 (1a-1c) and 2 (2a-2c) have been measured. The results show the complexes may be explored for potential luminescent materials.

Unsymmetrical Bicentric Organotin Lewis Acids {Me2N(CH2)3}Ph(X)Sn(CH2)nSnPh2X (X = F, I; n = 1, 3): Syntheses and Structures

The syntheses of the intramolecularly coordinated organotin compounds {Me2N(CH2)3}Ph(X)SnCH2SnPh2X (3, X = I; 4, X = F) and {Me2N(CH2)3}Ph(F)Sn(CH2)3SnPh2F (7) are reported. The compounds have been characterized by elemental analysis, electrospray mass spectrometry, 1H,1H DOSY (4), 13C, 19F, and 119Sn NMR spectroscopy, and single-crystal X-ray diffraction analysis. In the solid state, compound 4 is a head-to-tail dimer as a result of unsymmetrical Sn–F–Sn bridges, whereas compound 7 is a monomer with F→Sn intramolecular coordination, giving a six-membered ring. In solution, both 4 and 7 are monomeric. The reactions of both 4 and 7 with fluoride anion in CD2Cl2 have been investigated by variable-temperature 19F and 119Sn NMR spectroscopy.

Superspace description of trimethyltin hydroxide at T = 100 K

Abstract At low temperatures the metalorganic compound trimethyltin hydroxide, (CH3)3SnOH, possesses a commensurately modulated crystal structure, the modulation wave vector can be described as q = 1 2 c ∗ . ${\bf{q}}\; = \;{1 \over 2}{{\bf{c}}^ * }.$ The crystal structure is studied by analysing single-crystal X-ray diffraction data within the (3+1)-dimensional superspace approach and superspace group P21212(00γ)00s. The corresponding twofold superstructure has space group symmetry P212121. The structure is characterised by polymeric chains running along c-axis, generated by Sn–O–Sn bridges between neighbouring Sn atoms and packed in a distorted hexagonal pattern and linked via C–H···O interstrand hydrogen bonds along the (orthorhombic) directions [110] and [11̅0], but not along [100].

Synthesis, structure and cytotoxic activity of diethyltin N‐[(2‐oxyphenyl)methylene]phenylalaninates

Four new diethyltin N‐[(2‐oxyphenyl)methylene]phenylalaninates, (CH3CH2)2Sn[2‐O‐3‐X‐5‐YC6H2CHNCH(CH2Ph)COO] (X, Y = H, H, 1; H, Br, 2; H, OCH3, 3; Br, Br, 4), have been synthesized and characterized using elemental analysis and infrared and NMR (1H, 13C and 119Sn) spectra. The crystal structures of 1, 2, 3, 4 have been determined. Compounds 1 and 2 have a 12‐membered macrocyclic structure with a trimeric [Sn3O6C3] core. Each tin atom is six‐coordinated in distorted [SnC2NO3] octahedral geometry. Compound 3 is a centrosymmetric weak dimer in which the two tin centers are linked by two asymmetric SnO⋅⋅⋅Sn bridges involving the phenolic oxygen of the ligand and two Sn⋅⋅⋅O interactions from ether oxygen of the adjacent ligand. The coordination geometry of the tin atom can be described as a distorted pentagonal bipyramid with two ethyl groups in axial positions. Compound 4 is a novel binuclear tin complex, formed by the carboxylate of a ligand asymmetrically bridging two tin atoms, which contains a five‐coordinated tin and a six‐coordinated tin. Bioassay results have shown that the compounds have weak in vitro activity against two human tumor cell lines, A549 and CoLo205. Copyright © 2016 John Wiley & Sons, Ltd.

Interaction of organotin(IV) moieties with nucleic acid constituent: Synthesis, structural characterization and anti-inflammatory activity of tri-i-propyltin(IV) and diorganotin(IV) derivatives of guanosine

Abstract Tri- i -propyltin(IV) and diorganotin(IV) derivatives of guanosine of the general formulae, i -Pr 3 Sn(HGuO).H 2 O and [R 2 Sn(O)(HGuO).H 2 O] n , where R = Me, n -Oct and Ph; H 2 GuO = Guanosine, have been synthesized by either sodium salt or azeotropic removal of water method. The bonding and coordination behavior in these derivatives are discussed on the basis of FT-IR, multinuclear 1 H, 13 C and 119 Sn NMR and 119 Sn Mossbauer spectroscopic studies. These investigations suggest that guanosine acts as monoanionic monodentate coordinating through O-2′ of the ribofuranose group. Diorganotin(IV) derivatives of guanosine have a polymeric structure with Sn O Sn bridges and cis -disposition of the organic groups in a distorted trigonal-bipyramidal geometry around the tin atom. 119 Sn Mossbauer and 119 Sn NMR spectral data of tri- i -propyltin(IV) derivative support a penta-coordinate distorted trigonal-bipyramidal structure having equatorial organic groups, and involving a water molecule and O-2′ of the ribofuranose group in the axial positions. Some extent of intermolecular hydrogen-bonding involving water or (OH) groups leading to some degree of polymerization could not be ignored. Tri- i -propyltin(IV) and diorganotin(IV) derivatives of guanosine exhibited very low anti-inflammatory activity (~ 7.51–9.21% inhibition) at 40 mg kg − 1 dose and LD 50 values > 200 mg kg − 1 in albino rats.

Synthesis and Crystal Structure of One Trinuclear di-n-butyltin(IV) Complex with Salicylaldoxime

One trinuclear di-n-butyltin(IV) complex with salicylaldoxime (o-HON=CHC6H4OH=HONZOH), (Bu2Sn)(Bu2SnO)(Bu2SnOH)(ONZOH)(ONZO), has been synthesized and characterized by elemental analyses, IR spectrum, and single crystal X-ray diffraction. This complex is a small cluster displaying two unequivalent salicylaldoximate with one seven-coordinate pentagonal–bipyramidal tin atom linked two five-coordinate trigonal–bipyramidal tin atoms via a network of oxygen atoms by Sn–O–Sn bridges. The hydrogen bonds (o-HON=CHC6H4–O…H–O) are observed in the complex. These hydrogen bonds include intramolecular hydrogen bonds and intermolecular hydrogen bonds. (Bu2Sn)(Bu2SnO)(Bu2SnOH)(ONZOH)(ONZO) belongs to monoclinic: space group P21/n, with a = 12.2307(15) A, b = 17.361(2) A, c = 20.976(3) A, β = 94.424(2)°, V = 4440.5(10) A3, Z = 4, D c = 1.500 g/cm3, μ(MoKα) = 1.715 mm−1, F(000) = 2024, and final R 1 = 0.0426, wR 2 = 0.1064 for observed reflections 7779(I > 2σ(I)). The title compound, di-n-butyltin(IV) complex with salicylaldoxime, was synthesized and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that the molecular structure of the title compound is trinuclear. The complex is a small cluster displaying two unequivalent salicylaldoximate with one seven-coordinate pentagonal–bipyramidal tin atom linked two five-coordinate trigonal–bipyramidal tin atoms via a network of oxygen atoms by Sn–O–Sn bridges.

Bis(μ-2-pyridine-2,6-dicarboxylato)bis[aquadimethyltin(IV)

The title dinuclear complex, [Sn2(CH3)4(C7H3NO4)2(H2O)2], lies on a crystallographic inversion center. The unique SnIV atom is coordinated in a slightly disorted penta­gonal-bipyramidal geometry. The two symmetry-related SnIV atoms are connected via two asymmetric Sn—O—Sn bridges (Sn—O = 2.473 and 2.634 Å), such that an exactly planar Sn—O—Sn—O ring is formed.

Novel organotin(IV) compounds derived from bis(organostannyl)methanes: Synthesis and crystal structures of bis[diphenyl(pyridin-2-onato)stannyl]methane and bis[bromophenyl(pyrimidine-2-thionato)stannyl]methane · C 7H 8

Reaction between bis(chlorodiphenylstanyl)methane and the sodium salt of 2-hydroxypyridine (pyONa) in the molar ratio of 1:2 provides the organotin hydroxide derivative [Ph 2(pyO)SnCH 2Sn(OH)Ph 2] 2 ( 1) (where pyO = anion of 2-hydroxypyridine), while reaction of bis(dibromophenylstanyl)methane with the sodium salt of pyrimidine-2-thione (pmtNa) in molar ratio of 1:4 gives the corresponding organotin thiolate derivative, as its toluene solvate [BrPh(pmt)Sn] 2CH 2 · C 7H 8 ( 2) (where pmt = anion of pyrimidine-2-thione). Both compounds were characterized by single crystal X-ray diffraction analysis and contain five-coordinate tin atoms. Compound 1 is a centrosymmetric head-to-tail dimmer with almost symmetrical Sn(1)–O(H)–Sn(2A) bridges.

Synthesis and characterization of some monoorganotin(IV) chloride adducts with internally functionalized oximes: Crystal and molecular structures of nBuSnCl 3 · HON [dbnd]C(Me)Py-2 · C 6H 5Me and a trinuclear hydroxo bridged stannoxane { nBuSnCl 2(ON [dbnd]C(Me)Py-2)OH} 2Sn nBuCl · 0.5HON [dbnd]C(Me)Py-2

Reactions of RSnCl 3 (R = Et and n Bu) with internally functionalized oximes in 1:1 and 1:2 stoichiometric ratios in anhydrous benzene afforded non-ionic fibrous complexes of the general formula RSnCl 3 · nHON C(R′)Ar [R = Et and Bu; R′ = H, Me n = 1 and 2 ( 1– 8); R′ = only Me ( 9– 11); Ar = 2-NC 5H 4, 2-OC 4H 3. Except for 1:1 furyl derivative, the value of 119Sn chemical shifts for all these derivatives in the 119Sn NMR spectra suggests hexa-coordination around tin atom. The crystal and molecular structures of one of the adducts n BuSnCl 3 · HON C(Me)Py-2 · C 6H 5Me ( 2.tol.) and of a trinuclear hydroxo bridged stannoxane { n BuSnCl 2(ON C(Me)Py-2)OH} 2Sn n BuCl · 0.5 HON C(Me)Py-2 ( 12), obtained on hydrolysis of n BuSnCl 3 · 2HON C(Me)Py-2 ( 6), revealed a distorted octahedral environment around tin with the participation of both nitrogen atoms (ring as well as oxime nitrogen atom of the same ligand moiety) in coordination. In compound ( 2.tol.), the existence of intramolecular hydrogen bonding between the hydroxyl proton of the ligand moiety and the chlorine atom stabilizes the geometry. Unique asymmetric Sn–O(H)–Sn and Sn–O–N–Sn bridges are present in compound ( 12), resulting in a linear trinuclear stannoxane framework.

Self-assembly of diorganotin(IV) 2-{[( E)-1-(2-oxyaryl)alkylidene]amino}acetates: An investigation of structures by X-ray diffraction, solution and solid-state tin NMR, and electrospray ionization MS

The diorganotin(IV) compounds, [Me 2SnL 2(OH 2)] 2 ( 1), [ n Bu 2SnL 2(OH 2)] 2 ( 2), [ n Bu 2SnL 1] 3 · 0.5C 3H 6O ( 3), [ n Bu 2SnL 3] 3 · 0.5C 6H 6 ( 4) and [Ph 2SnL 3] n · 0.5C 6H 6 ( 5) (L = carboxylic acid residue, i.e., 2-{[( E)-1-(2-oxyaryl)alkylidene]amino}acetate), were synthesized by treating the appropriate diorganotin(IV) dichloride with the potassium salt of the ligand in anhydrous methanol.The reaction of Ph 2SnL 2 (L = 2-{[( E)-1-(2-oxyphenyl)ethylidene]amino}acetate) with 1,10-phenanthroline (Phen) yielded a 1:1 adduct of composition, [Ph 2SnL 2(Phen)] ( 6).The crystal structures of 1– 6 were determined.The crystal of 1 is composed of centrosymmetric dimers of the basic Me 2SnL 2(OH 2) moiety, where the two Sn-centres are linked by two asymmetric Sn–O⋯Sn bridges involving the carboxylic acid O atom of the ligand and a long Sn⋯O distance of 3.174(2) Å.The dimers are further linked into columns by hydrogen bonds.The coordination geometry about the Sn atom is a distorted pentagonal bipyramid with the two methyl groups in axial positions.The structure of 2 is similar.The same Sn atom coordination geometry is observed in compound 3, which is a cyclic trinuclear[ n Bu 2SnL 1] 3 compound. Each Sn atom is coordinated by the phenoxide O atom, one carboxylate O atom and the imino N atom from one ligand and both the exo- and endo-carboxylate O atoms (mean Sn–O( exo): 2.35 Å; Sn–O( endo): 2.96 Å) from an adjacent ligand to form the equatorial plane, while the two butyl groups occupy axial positions. Compound 4 was found to crystallize in two polymorphic forms. The Sn-complex in both forms has a trinuclear [ n Bu 2SnL 3] 3 structural motif similar to that found in 3. In compound 5, distorted trigonal bipyramidal Ph 2SnL 3 units are linked into polymeric cis-bridged chains by a weak Sn⋯O interaction (3.491(2) Å) involving the exocyclic O atom of the tridentate ligand of a neighboring Sn-complex unit. This interaction completes a highly distorted octahedron about the Sn atom, where the weakly coordinated exocyclic O atom and one phenyl group are trans to one another. In contrast, a monomeric distorted pentagonal bipyramidal geometry is found for adduct 6 where the Sn-phenyl groups occupy the axial positions. The solution and solid-state structures are compared by using 119Sn NMR chemical shift data. Compounds 1– 6 were also studied using ESI-MS and their positive- and negative-ions mass fragmentation patterns are discussed.

Synthesis and Reactivity of [2]Ferrocenophanes with C−Ge and C−Sn Bridges

The synthesis, characterization, and reactivity of novel carbogerma[2]ferrocenophanes, (η-C5Me4)Fe(η-C5H4)CH2GeR2, 11 (a, R = Ph; b, R = Me), and carbostanna[2]ferrocenophanes, (η-C5Me4)Fe(η-C5H4)CH2SnR2, 12 (a, R = tBu; b, R = Mes; c, R = Me), are reported. Compounds 11a,b and 12a−c were isolated as orange crystals from the reaction of (η-C5Me4)Fe(η-C5H4Li)CH2Li·xTMEDA with Cl2ER2 (E = Ge, R = Ph, Me or E = Sn, R = tBu, Mes, Me) and were characterized by 1H, 13C, and 119Sn NMR, UV/vis, MS, and in representative cases elemental analysis. X-ray diffraction analysis of these species revealed structures possessing moderate ring-tilt with values in the range α = 10.99(2)−11.81(5)° for 11a,b and α = 6.64(2)−7.5(1)° for 12a−c. The presence of a small or moderate degree of ring-strain was further substantiated through the observation of only a small (ca. 25−30 nm) bathochromic shift in the UV/vis absorption maxima when compared to pentamethylferrocene. Attempts to induce thermal ring-opening polymerization (ROP)...

In Situ Synthesis of Polysulfides Covalently Bonded to Silica

Silanol groups, SiOH, on the surface of silica were esterified with unsaturated alcohols and long-chain alcohols bearing thiol groups. The modified silicas obtained were used as substrates for a vulcanization-analogous reaction with sulfur catalyzed by zinc dimethyldithiocarbamate. Surface-esterified thiols could be smoothly converted to bridged polysulfides bonded to the silica surface, whereas the use of surface-esterified unsaturated alcohols led to removal of the surface-esterified alcohol from the silica surface. The materials were characterized by solid-state NMR and thermal and microanalytical analysis. The linking of surface-esterified alkenols and thiols by sulfide bridges was investigated by a numerical model for a flat surface. This showed that for a typical density of 3–4 μmol/m2 surface groups, a statistical maximum of 70–75% of groups could be linked by Sn bridges (n=2–4).

Synthesis and structural behavior of the P-functional organotin chlorides [Ph 2P(CH 2) 3] 2SnCl 2, Ph 2P(CH 2) 3SnCl 2Me, and Ph 2P(CH 2) nSnCl 3 ( n=2, 3)

The P-functional organotin dichloride [Ph 2P(CH 2) 3] 2SnCl 2 ( 3) is synthesized by reaction of Ph 2P(CH 2) 3MgCl with SnCl 4 independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph 2P(CH 2) n SnCl 2R ( 4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph 2P(CH 2) n SnCy 3 ( n=2, 3) with SnCl 4 or MeSnCl 3, respectively. The main features of the crystal structures of 3– 6 are both intra- and intermolecular P⋯Sn coordinations and the existence of intermolecular SnCl⋯Sn bridges. For further characterization of the title compounds, the adducts 4(Ph 3PO) 2 ( 7) and 5(Ph 3PO) ( 8), as well as the P-oxides and P-sulfides of 3– 6 ( 9– 15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9– 15 are characterized by intramolecular P=X⋯Sn interactions (X=O, S). A first insight into the structural behavior of the compounds 3– 15 in solution is discussed on the basis of multinuclear NMR data.

Cyclo-CH2{Sn(Cl2)CH2Si(Me2)}2O]: Synthesis and Complexation Behaviour of a Novel, Cyclic, Bidentate Lewis Acid and Its Conversion into a Tin-Containing Fluorosilane with Intermolecular Si−F⋅⋅⋅Sn Bridges

cyclo-CH2{Sn(Cl2)CH2Si(Me2)}2O]: Synthesis and Complexation Behaviour of a Novel, Cyclic, Bidentate Lewis Acid and Its Conversion into a Tin-Containing Fluorosilane with Intermolecular Si−F⋅⋅⋅Sn Bridges

Cyclo-CH2[Sn(CI2)CH2Si(Me2)]2O]: synthesis and complexation behaviour of a novel, cyclic, bidentate Lewis acid and its conversion into a tin-containing fluorosilane with intermolecular Si-F...Sn bridges.

Acid-catalysed hydrolysis of [CH2[(Sn(Ph2)CH2Si(OiPr)Me2]2] followed by subsequent reaction with mercuric chloride in acetone afforded the novel silicon- and tin-containing eight-membered ring [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] in good yield, the crystal structure of which is reported. 119Sn NMR and X-ray studies indicate that [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] acts as a bidentate Lewis acid towards chloride ions exclusively forming the 1:1 complex [(Ph3P)2N]+[cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2OCl]- upon addition of [(Ph3P)2N]+Cl- . Also reported are the synthesis and structure of [K(dibenzo[18]crown-6)]+[cyclo-CH2(Sn(Cl2)CH2Si(Me2)]2OF]-, the first completely characterised organostannate with a C2SnCl2F- substituent pattern. No ring-opening polymerisation could be achieved for [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] or for its perphenylated derivative [cyclo-CH2[Sn(Ph2)CH2Si(Me2)]2O]. The reaction of [cyclo-CH2[Sn(Cl2)CH2Si(Me2)]2O] with Me3O+BF4- gave the tin-containing fluorosilane [CH2[Sn(Cl2)CH2Si(F)Me2]2], in which the Si-F bond is activated by intermolecular Si-F...Sn interactions in the solid state.

Synthesis, Structure, Electrochemistry and Reactivity of the Bis(μ-σ-stannanediyl)dinickel Butterfly Cluster [{{(SiMe3)2CH}2Sn–Ni(η5-Cp)}2](Ni2–Sn2)

Addition of stannylene [{(SiMe3)2CH}2Sn:] (2) to the unbridged homobimetallic Ni–Ni bond of [{PEt3Ni(η5-Cp)}2] (1) gives the heterobimetallic, tetranuclear compound [{{(SiMe3)2CH}2Sn–Ni(η5-Cp)}2] (3) with a butterfly arrangement and leaves the Ni–Ni bond of 1 intact. Elimination of both PEt3 ligands from the starting material 1 is observed, probably due to steric restraints. Compound 3 is formally related to the hypothetical closo-borane B4H42–. The Ni–Ni bond in 3 is only slightly elongated [2.454(3) Å] when compared to the starting material 1 [2.41(1) Å]. Compound 3 displays a butterfly arrangement with a hinge angle of 62.5°. An alternative route to 3 is by a direct reaction between nickelocene (5) and Lappert's stannylene [{(SiMe3)2CH}2Sn:] in 63% yield. Treating 3 with water results in the cleavage of an Ni–Sn bond and subsequent opening of the cluster cage of 3 to form the trinuclear compound [(η5-Cp)Ni{Sn(CH(SiMe3)2}2OH] (6) having an Sn–OH–Sn bridge. The hydroxy proton in 6 can be exchanged by deuterium within a few minutes, as determined by 1H-NMR spectroscopy, giving the monodeuterio product, [D1]-6. Compound 6 is reactive towards acetonitrile, leading to cleavage of one Ni–Sn bond, elimination of one [{(SiMe3)2CH}2Sn:] unit, and formation of the organotin hydroxo complex [{(SiMe3)2CH}2(OH)Sn–Ni(η5-Cp)(CH3CN)] (7). In this complex, acetonitrile is coordinated to Ni via its σ lone pair, bearing the OH ligand in a terminal bonding mode to tin.

CuCN.Me(3)SnCN.0.5bpy] (bpy = 4,4'-Bipyridine): A Novel Supramolecular Assembly Involving the No Longer Unusual {Cu(2)(&mgr;-CN)(2)(CN)(2)} Motif.

Reaction of K(3)[Cu(CN)(4)] with Me(3)SnCl and 4,4'-bipyridine (bpy) affords the novel ternary adduct [CuCN.Me(3)SnCN.0.5bpy], 2, as yellow, cubelike crystals. The supramolecular architecture of 2 consists, according to a single-crystal X-ray study, of remarkably porous, approximately planar sheets held together by almost perpendicular bpy pillars. Basic building blocks of the sheets are {Cu(2)(&mgr;-CN)(2)(CN)(2)} fragments whose N atoms are connected, via Me(3)Sn bridges, with the N atoms of adjacent fragments. 2 crystallizes in space group P2(1)/c with (at 20 degrees C) a = 10.035(4) Å, b = 11.980(3) Å, c = 12.425(5) Å, beta = 110.94(3) degrees, and Z = 4. The dinuclear building blocks resemble strongly those of the long known, but chemically more labile, layered coordination polymer [CuCN.NH(3)], 1. Although the lattice of 2 consists of two equivalent, ideally interpenetrating 3D frameworks, spacious, straight channels of a cross section of ca. 10 Å x 5 Å persist in this unprecedented structure. The likewise polymeric new adduct [CuCN.Me(3)SnCN.H(2)O] (3) obtained from K(3)[Cu(CN)(4)] and Me(3)SnCl in the absence of bpy may be considered as a formal precursor of 2.

Base‐Induced Synthesis of a Tetrastannatriazabicyclo[3.1.1]heptane from Tris)dimethylchlorostannyl)amine

AbstractTris(dimethylchlorostannyl)amine (2a) reacts with pyridine in a 3:4 molar ratio to produce the tin‐nitrogen containing bicyclo[3.1.1]heptane (3) with elimination of the adduct Me2SnCl2·2 py. Treatment of the distannylamine 2,6‐[Pr2H3N(SnMe2Cl)2 (4) with pyridine, however, leads to the formation of the 1:1 pyridine adduct 4 and this can be regarded as a model to explain the route to 3. The molecular structures of 3 and 5 were determined by multinuclear magnetic resonance spectroscopy in solution, as well as by X‐ray structure analysis of their crystals. Typical structural features for both compounds are intramolecular SnXSn bridges. Support for the structures comes from MS fragmentation patterns, IR spectra, and the Mössbauer spectra.

Metal-oxygen versus metal-sulfur bonding of the ambident monothiophosphinato ligand in some triphenylmeta(IV) derivatives, Ph 3M[OSPR 2] (M = Ge, Sn, Pb). Crystal structures of Ph 3Ge[O(S)PPh 2] and [Ph 2Sn{O(S)PPh 2} (μ-OH)] 2

Diorganomonothiophosphinato-triphenylmetal(IV) derivatives, Ph 3M(OSPR @) (M = Ge, Sn, Pb; R = Me, Et, Ph), were prepared and investigated. The IR and multinuclear ( 1H, 13C, 31P) NMR spectra are discussed in relation to the MO and/or MS bonding of the ambident OSPR 2 − ligand. The crystal and molecular structures of Ph 3Ge[O(S)PPh 2] ( 1) and [Ph 2Sn{O(S)PPh 2} (μ-OH)] 2 ( 2) were determined by X-ray diffractometry. The asymmetric unit for Ph 3Ge[O(S)PPh 2] contains two independent molecules. The monothiophosphinato group is bonded to germanium only through oxygen (av. GeO 1.826, Ge···S 3.892 Å), leading to a tetrahedral coordination around the germanium atom. The crystal of [Ph 2Sn{O(S)PPh 2} (μ-OH)] 2 consists of dimeric units built up through SnOSn bridges involving the oxygen atom of the hydroxy groups. The monothiophosphinato group is again monodentate [Sn(1)O(1) 2.089(3), Sn(1)···S(1) (non-bonding) 4.164 Å] and the coordination geometry around tin is trigonal bipyramidal, with the O(1) atom of the phosphorus ligand and the O(2′) atome of a bridging hydroxy group in axial positions.