四个基于酰腙配体的双核苄基锡配合物的合成、晶体结构及体外抗癌活性

通过微波"一锅法"合成了4个双核苄基锡配合物:{[C_4H_3S(O)C=N-N=C(Me)COO](PhCH_2)_2Sn(MeOH)}_2(C1)、{[C_4H_3S(O)C=NN=C (Me)COO](p-Cl-C_6H_4CH_2)_2Sn (MeOH)}_2(C2)、{[C_4H_3S (O)C=N-N=C (PhCH_2)COO](PhCH_2)_2Sn (MeOH)}_2(C3)、{[C_4H_3S (O)C=N-N=C(PhCH_2)COO](p-Cl-C_6H_4CH_2)_2Sn(MeOH)}_2(C4),利用元素分析、IR、~1H NMR、~(13)C NMR、~(119)Sn NMR、HRMS以及X射线单晶衍射等表征了配合物结构。4个配合物分子均为双锡核分子,以Sn_2O_2四元环为中心对称,且中心锡原子与配位原子形成七配位畸变五角双锥构型。测试了配合物C1～C4的热稳定性以及配合物对癌细胞H460、HepG2、MCF7的体外抑制活性,结果表明:配合物C2是4个新合成的配合物中抑制癌细胞效果最好的化合物。     

Syntheses,crystal structures and biological activity of the dialkytin complexes based on 2-oxo-3-phenylpropionic acid salicyloylhydrazone

Three new dialkytin complexes, {[o-OH–C₆H₄(O)C=N–N=C(CH₂Ph)COO](n-Bu₂Sn)}_n (1), {[o-OH–C₆H₄(O)C=N–N=C(CH₂Ph)COO](MeOH)(p-MeC₆H₅CH₂)₂Sn}₂ (2), and {[o-OH–C₆H₄(O)C=N–N=C(CH₂Ph)COO](EtOH)(C₆H₅CH₂)₂Sn}₂ (3), were synthesized by reactions of 2-oxo-3-phenylpropionic acid salicyloylhydrazone with the corresponding diorganotin(IV) complex, respectively. All the complexes were characterized by IR, ¹H, ¹³C, ¹¹⁹Sn NMR spectra, elemental analysis, X-ray single crystal diffraction and TGA. For in vitro antitumor activities, complexes were evaluated by the MTT assay against three human cancer cell lines (NCI-H460, HepG2 and MCF7) and human cell line (HL7702). The results showed that 1 may be a better potential candidate for further chemical optimization and cancer therapy than 2 and 3. The interactions between the complexes and calf thymus DNA were studied; the interaction of 1 with calf thymus DNA was intercalation, 2 and 3 were intercalation and electrostatic binding.     

Synthesis and structural characterization of diorganotin(IV) complexes with 2,6‐pyridinedicarboxylic acid

Two new diorganotin(IV) derivatives of 2,6‐pyridinedicarboxylic acid, {[Ph₂Sn(2,6‐C₅H₃N)(COO)₂][Na(2,6‐C₅H₃N)(COOH) (COO)(CH₃OH)₂]} ( 1 ) and [Me₂Sn(2,6‐C₅H₃N)(COO)₂(H₂O)]^•H₂O ( 2 ) were synthesized by the reaction of Ph₃SnCl and PhMe₂SnI with 2,6‐pyridinedicarboxylic acid, respectively in the presence of sodium methoxide or potassium iso‐propoxide. The prepared compounds were characterized by mass spectrometry, IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopies. The molecular structures of both complexes were determined by a single‐crystal X‐ray analysis. The X‐ray structure revealed pentagonal bipyramidal geometry around the tin atom for compound 1, which is incorporated with a hexacoordinated monosodium derivative of 2,6‐pyridinedicarboxylic acid. Complex 2 adopts a monomeric structure with two carboxylate oxygen atoms coordinated to tin in monodenate form from equatorial positions, and the coordination number is raised to six as the oxygen of water and pyridine nitrogen occupies the other equatorial positions of octahedron. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and Characterization of 1,3,2‐Bis (arylamino) phospholidine, 2‐oxide Derivatives: Crystal Structures of $\rm Cl(O)\overline{PN(p-Me-C_{6}H_{4})CH_{2}CH_{2}N}(p-Me-C_{6}H_{4})$ and $\rm ((CH_{2}C_{6}H_{5})(O)\overline{PN(p-Me-C_{6}H_{4})CH_{2}CH_{2}N}(p-Me-C_{6}H_{4})$

Using phosphoryl chloride as a substrate, a family of 1,3,2‐bis(arylamino) phospholidine, 2‐oxide of the general formula ; (X=Cl, 6a ; X=NMe₂, 1b ; X=N(CH₂C₆H₅)(CH₃), 2b ; X=NHC(O)C₆H₅, 3b ; X=4Me‐C₆H₄O, 4b ; X=C₆H₅O, 5b ; X=NHC₆H₁₁, 6b ; X=OC₄H₈N, 7b ; X=C₅H₁₀N, 8b ; X=NH₂, 9b ; X=F, 10b and Ar=4Me‐C₆H₄) was prepared and characterized by ¹H, ¹⁹F, ³¹P and ¹³C NMR and IR spectroscopy, and elemental analysis. A general and practical method for the synthesis of these compounds was selected. The structures of 6a and 2b were determined by single‐crystal X‐ray diffraction techniques. The low temperature NMR spectra of 2b revealed the restricted rotation of P‐N bond according to two independent molecules in crystalline lattice.     

Gemischte Sandwichkomplexe der 4 f‐Elemente: Enantiomerenreine Cyclooctatetraenyl‐Cyclopentadienyl‐Komplexe des Samariums und Lutetiums mit donorfunktionalisierten Cyclopentadienylliganden

Organometallic Compounds of the Lanthanides. 139 Mixed Sandwich Complexes of the 4 f Elements: Enantiomerically Pure Cyclooctatetraenyl Cyclopentadienyl Complexes of Samarium and Lutetium with Donor‐Functionalized Cyclopentadienyl Ligands The reactions of [K{(S)‐C₅H₄CH₂CH(Me)OMe}], [K{(S)‐C₅H₄CH₂CH(Me)NMe₂}] and [K{(S)‐C₅H₄CH(Ph)CH₂NMe₂}] with the cyclooctatetraenyl lanthanide chlorides [(η⁸‐C₈H₈)Ln(μ‐Cl)(THF)]₂ (Ln = Sm, Lu) yield the mixed cyclooctatetraenyl cyclopentadienyl lanthanide complexes [(η⁸‐C₈H₈)Sm{(S)‐η⁵ : η¹‐C₅H₄CH₂CH(Me)OMe}] ( 1 a ), [(η⁸‐C₈H₈)Ln{(S)‐η⁵ : η¹‐C₅H₄CH₂CH(Me)NMe₂}] (Ln = Sm ( 2 a ), Lu ( 2 b )) and [(η⁸‐C₈H₈)Ln{(S)‐η⁵ : η¹‐C₅H₄CH(Ph)CH₂NMe₂}] (Ln = Sm ( 3 a ), Lu ( 3 b )). For comparison, the achiral compounds [(η⁸‐C₈H₈)Ln{η⁵ : η¹‐C₅H₄CH₂CH₂NMe₂}] (Ln = Sm ( 4 a ), Lu ( 4 b )) are synthesized in an analogous manner. ¹H‐, ¹³C‐NMR‐, and mass spectra of all new compounds as well as the X‐ray crystal structures of 3 b and 4 b are discussed.     

Synthesis and Characterization of Diphenyltin(IV) Dicarboxylates Containing Germanium

Twelve new germanium substituted diphenyltin dipropionates with the general formula (R¹GeCHR²‐CHR³COO)₂SnPh₂ where R¹ = N(CH₂CH₂O)₃, (C₆H₅)₃ and (CH₃C₆H₄)₃, R² = H, CH₃, C₆H₅, p‐CH₃C₆H₄, p‐CH₃OC₆H₄, p‐ClC₆H₄, and R³ = H, CH₃ have been synthesized by the reaction of diphenyltin oxide with a germanium substituted propionic acid. All the compounds were characterized by elemental analysis, IR, multi‐nuclear (¹H, ¹³C, ¹¹⁹Sn) NMR and Mössbauer spectroscopies as well as mass spectrometry. The in vitro antibacterial activity of selected compounds is also reported.     

Water Soluble Gold(I)‐diacetyl‐1,3,5‐triaza‐7‐phosphaadamantane‐arylazoimidazole Complexes: Synthesis and Spectroscopic Study

Reaction of [Au(DAPTA)(Cl)] with RaaiR’ in CH2Cl2 medium following ligand addition leads to [Au(DAPTA)(RaaiR’)](Cl) [DAPTA＝diacetyl-1,3,5-triaza-7-phosphaadamantane, RaaiR’＝p-R-C6H4-N＝N- C3H2-NN-1-R’, (1—3), abbreviated as N,N’-chelator, where N(imidazole) and N(azo) represent N and N’, respectively; R＝H (a), Me (b), Cl (c) and R’＝Me (1), CH2CH3 (2), CH2Ph (3)]. The 1H NMR spectral measurements in D2O suggest methylene, CH2, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. 13C NMR spectrum in D2O suggest the molecular skeleton. The 1H-1H COSY spectrum in D2O as well as contour peaks in the 1H-13C HMQC spectrum in D2O assign the solution structure.     

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.     

β-Diketiminato Rare-Earth Metal Complexes: The Influence of Monoatomic Substituents in the N-aryl Moieties on Structures and Properties

Treatment of β-diketiminate ligands bearing different N-aryl monoatomic substituents [HL^H = (C₆H₅)N = C(Me)CH=C(Me)NH(C₆H₅), HL^F = (2,6-F₂C₆H₃)N=C(Me)CH=C(Me)NH(2,6-F₂C₆H₃), and HL^Cl = (2,6-Cl₂C₆H₃)N=C(Me)CH=C(Me)NH(2,6-Cl₂C₆H₃)] with Ln(CH₂SiMe₃)₃(THF)₂ (Ln = Y and Lu) afforded a variety of β-diketiminato rare-earth metal complexes depending on substituents, namely, phenyl ring C–H bond activated complexes (L')(L^H)Lu(THF) ( 1b , L' = (C₆H₄)N = C(Me)CH=C(Me)N(C₆H₅)), six-coordinate homoleptic complexes (L^H)₃Ln [Ln = Y ( 1aa ), Lu ( 1bb )], five-coordinate monoalkyl complexes (L^F)₂Ln(CH₂SiMe₃) [Ln = Y ( 2a ), Lu ( 2b )], and four-coordinate dialkyl complexes (L^Cl)Ln(CH₂SiMe₃)₂ [Ln = Y ( 3a ), Lu ( 3b )]. All these complexes were characterized with NMR spectroscopy, and lutetium complexes 1b , 1bb and 3b were structurally validated by single-crystal X-ray diffraction analysis. Moreover, dialkyl complexes 3 promoted the polymerization of 2-vinylpyridine (2-VP) to produce atactic poly(2-vinylpyridine) (P2VP) with quantitative yield. On activation with an equimolar amount of [Ph₃C][B(C₆F₅)₄], complexes 3 afforded highly isotactic P2VP with an mm value up to 94 %. Both ¹H NMR spectrum and MALDI-TOF mass analysis of an oligomer indicate that the polymerization was initiated by coordination insertion of 2-VP into the Y-CH₂SiMe₃ bond.     

Reactivity of TpMe2‐Supported Yttrium Alkyl Complexes toward Aromatic N‐Heterocycles: Ring‐Opening or CC Bond Formation Directed by CH Activation

Unusual chemical transformations such as three‐component combination and ring‐opening of N‐heterocycles or formation of a carbon–carbon double bond through multiple C–H activation were observed in the reactions of Tp^Me2‐supported yttrium alkyl complexes with aromatic N‐heterocycles. The scorpionate‐anchored yttrium dialkyl complex [Tp^Me2Y(CH₂Ph)₂(THF)] reacted with 1‐methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24‐membered rare‐earth metallomacrocyclic compound [Tp^Me2Y(μ‐N,C‐Im)(η²‐N,C‐Im)]₆ ( 1 ; Im=1‐methylimidazolyl) through two kinds of C–H activations at the C2‐ and C5‐positions of the imidazole ring. However, [Tp^Me2Y(CH₂Ph)₂(THF)] reacted with two equivalents of 1‐methylbenzimidazole to afford a C–C coupling/ring‐opening/C–C coupling product [Tp^Me2Y{η³‐(N,N,N)‐N(CH₃)C₆H₄NHCH?C(Ph)CN(CH₃)C₆H₄NH}] ( 2 ). Further investigations indicated that [Tp^Me2Y(CH₂Ph)₂(THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C–C coupling/ring‐opening product {(Tp^Me2)Y[μ‐η²:η¹‐SC₆H₄N(CH?CHPh)](THF)}₂ ( 3 ). Moreover, the mixed Tp^Me2/Cp yttrium monoalkyl complex [(Tp^Me2)CpYCH₂Ph(THF)] reacted with two equivalents of 1‐methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [Tp^Me2CpY(μ‐N,C‐Im)]₃ ( 5 ), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [Tp^Me2Y(Im‐Tp^Me2)] ( 7 ; Im‐Tp^Me2=1‐methyl‐imidazolyl‐Tp^Me2) and [Cp₃Y(HIm)] ( 8 ; HIm=1‐methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a C?C bond through multiple C–H activations.     

Germylenes and stannylenes based on aminobisphenolate ligands: insertion into the C—Br bond

A reaction of previously synthesized germylenes and stannylenes based on aminobisphenols RN{CH₂[(5-R´)(3-But)C₆H₂(2-O—)]}₂M^II, M = Ge, R = CH²(2-Py), R´ = But (1); M = Ge, R = Et, R´ = Me (2); M = Sn, R = CH₂(2-Py), R´ = But (3); M = Sn, R = Et, R´ = Me (4), containing (tetrylenes 1 and 3) or not containing (tetrylenes 2 and 4) a group capable of additional donation, with allyl bromide leads to the products of the insertion of tetrylenes into the C—Br bond: RN{CH₂[(5-R´)(3-Bu^t)C₆H₂(2-O—)]}₂M(Br)All, M = Ge, R = CH₂(2-Py), R´ = But (5); M = Ge, R = Et, R´ = Me (6); M = Sn, R = CH₂(2-Py), R´ = But (7); M = Sn, R = Et, R´ = Me (8). The structures of obtained derivatives were confirmed by NMR spectroscopy and elemental analysis. The structures of compounds 4, 5, and 7 were studied by X-ray crystallography. Stannylene 4 was found to be monomeric in the solid phase: the coordination number of the Sn atom is 3. The insertion products 5 and 7 are characterized by the coordination number 6 for the central atom.     

Synthese und Struktur C,N‐difunktionalisierter Sulfinimidamide

Synthesis and Structure of C,N‐difunctionalized Sulfinimideamides Sulfurdiimides RN=S=NR ( 1 a , b ) react in diethyl ether with two equivalents of lithiummethyl to give dimeric C,N‐dilithiummethylenesulfinimideamide ether adducts {Li₂[H₂C–S(NR)₂ · Et₂O]}₂ ( 2 a , b ) ( a : R = ^tBu, b : R = SiMe₃). Metathesis of 2 b with four equivalents of Me₃SiCl, Me₃SnCl or Ph₃SnCl yields the corresponding C,N‐bis‐substituted sulfinimideamides R₃EH₂C–S[N(SiMe₃)₂]NER₃ ( 3 – 5 ) ( 3 : R = Me, E = Sn; 4 : R = Ph, E = Sn; 5 : R = Me, E = Si). The crystal structures of 2 a and 2 b were determined by X‐ray structure analysis. Both compounds form centrosymmetric cage structures consisting of two distorted face sharing cubes ( 2 a : space group P1 (No. 2); Z = 2 (4 · 0,5); 2 b : space group C2/c (No. 15), Z = 4).     

Poly(ethylene terephthalate) synthesis catalysed by chelated Sn,Zn and Mg complexes

A series of four C,N‐chelated diorganotin(IV) compounds, namely (L^CN)₂Sn(OCH₂CH₂O) ( 1 ), [L^CNBuSn(OCH₂CH₂O)]₂ ( 2 ), (L^CN)₂Sn(1,2‐(O)₂‐3,5‐tBu₂C₆H₂) ( 3 ) and [L^CNBuSn(1,2‐(O)₂‐3,5‐tBu₂C₆H₂)]₂ ( 4 ) (L^CN = 2‐(Me₂NCH₂)C₆H₄), one zinc species, namely L^NOZnEt ( 5 ) (L^NO = [2‐(MeO)C₆H₄]NC(Me)?C(H)C(Me)?O), and one magnesium complex, namely [L^NNMg]₆ ( 6 ), (L^NN = [2‐(Me₂NCH₂)C₆H₄]N), were used as catalysts for the synthesis of poly(ethylene terephthalate) (PET) from dimethyl terephthalate and ethylene glycol. Prepared PET samples were primarily characterized using the size exclusion chromatography technique. The highest number‐average molar mass of prepared PET samples reached 10.7 kg mol^?1. Novel dimeric compound 2 was structurally characterized using both multinuclear NMR spectroscopy and X‐ray diffraction analysis. In addition, an alternative synthesis of 1 is described. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis,spectral and antimicrobial studies of diorganotin(IV)3(2′‐hydroxyphenyl)‐5‐(4‐substituted phenyl) pyrazolinates

Diorganotin(IV) dipyrazolinates of the type R₂Sn(C₁₅H₁₂N₂OX)₂ [where C₁₅H₁₂N₂OX = 3(2′‐Hydroxyphenyl)‐5(4‐X‐phenyl)pyrazoline {where X = H ( a ); CH₃ ( b ); OCH₃ ( c ); Cl ( d ) and R = Me, Prⁿ and Ph}] have been synthesized by the reaction of R₂SnCl₂ with sodium salt of pyrazolines in 1:2 molar ratio, in anhydrous benzene. These newly synthesized derivatives have been characterized by elemental analysis (C, H, N, Cl and Sn), molecular weight measurement as well as spectral [IR and multinuclear NMR (¹H, ¹³C and ¹¹⁹Sn)] studies. The bidentate behaviour of the pyrazoline ligands was confirmed by IR, ¹H and ¹³C NMR spectral data. A distorted trans‐octahedral structure around tin(IV) atom for R₂Sn(C₁₅H₁₂N₂OX)₂ has been suggested. The free pyrazoline and diorganotin(IV) dipyrazolinates have also been screened for their antibacterial and antifungal activities. Some diorganotin(IV) dipyrazolinates exhibit higher antibacterial and antifungal effect than free ligand and some of the antibiotics. Copyright © 2006 John Wiley & Sons, Ltd.     

Self‐Assembly of Dialkyltin Moieties and Mercaptobenzoic Acid into Macrocyclic Complexes with Hydrophobic “Pseudo‐Cage” or Double‐Cavity Structures: Supramolecular Infrastructures Involving Intermolecular C?H⋅⋅⋅S Weak Hydrogen Bonds and π–π Interactions

Four novel organotin complexes of two types—[R₂Sn(o‐SC₆H₄CO₂)]₆ (R=Me, 1 ?H₂O; nBu, 2 ) and {[R₂Sn(m‐CO₂C₆H₄S)R₂Sn(m‐SC₆H₄CO₂)SnR₂]O}₂ (R=Me, 3 ; nBu, 4 )—have been prepared by treatment of o‐ or m‐mercaptobenzoic acid and the corresponding R₂SnCl₂ (R=Me, nBu) with sodium ethoxide in ethanol (95 %). All the complexes were characterized by elemental analysis, FT‐IR and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy, TGA, and X‐ray crystallography diffraction analysis. The molecular structure analyses reveal that both 1 and 2 are hexanuclear macrocycles with hydrophobic “pseudo‐cage” structures, while 3 and 4 are hexanuclear macrocycles with double‐cavity structures. Furthermore, the supramolecular structure analyses show that looser and more intriguing supramolecular infrastructures were also found in complexes 1 – 4 , which exist either as one‐dimensional chains of rings or as two‐dimensional networks assembled from the organometallic subunits through intermolecular C? H???S weak hydrogen bonds (WHBs) and π–π interactions.     

丙酮酸异烟酰腙四核有机锡配合物的合成、表征及{[nBu2Sn(C9H8N3O3)O]SnBu3n}2的晶体结构

The tetranuclear alkyltin(Ⅳ) compounds {[R2Sn(C9H8N3O3)O]SnR3}2 [R=n-Bu (1), 4-CNC6H4CH2 (2),C6H5CH2 (3), 4-ClC6H4CH2 (4)] were prepared by the reaction of Schiff base ligand pyruvic acid isonicotinyl hydrazone with (R3Sn)2O in the corresponding molar ratio of 1:1. All compounds have been characterized by elemental analysis, IR and ^1H NMR spectra. The crystal structure of compound 1 was determined by X-ray single crystal diffractional analysis. This compound exhibits a dimeric structure containing distannoxane units with two types of the tin atoms. For the first tin atom, it appears to be seven-coordinated with a distorted pentagonal bipyramid geometry, and the other is five-coordinated with a distorted trigonal bipyramidal geometry. The molecules are packed in the unit cell in two-dimensional network structure through an interaction between the N atoms of the pyridine and the tin atoms of an adjacent molecule.     

Construction of tetranuclear macrocycles through C-H activation and structural transformation induced by [2+2] photocycloaddition reaction

A series of binuclear complexes [{Cp*Ir(OOCCH₂COO)}₂(pyrazine)] ( 1 b ), [{Cp*Ir(OOCCH₂COO)}₂(bpy)] ( 2 b ; bpy=4,4′‐bipyridine), [{Cp*Ir(OOCCH₂COO)}₂(bpe)] ( 3 b ; bpe=trans‐1,2‐bis(4‐pyridyl)ethylene) and tetranuclear metallamacrocycles [{(Cp*Ir)₂(OOC‐C?C‐COO)(pyrazine)}₂] ( 1 c ), [{(Cp*Ir)₂(OOC‐C?C‐COO)(bpy)}₂] ( 2 c ), [{(Cp*Ir)₂(OOC‐C?C‐COO)(bpe)}₂] ( 3 c ), and [{(Cp*Ir)₂[OOC(H₃C₆)‐N?N‐(C₆H₃)COO](pyrazine)}₂] ( 1 d ), [{(Cp*Ir)₂[OOC(H₃C₆)‐N?N‐(C₆H₃)COO](bpy)}₂] ( 2 d ), [{(Cp*Ir)₂[OOC(H₃C₆)‐N?N‐(C₆H₃)COO](bpe)}₂] ( 3 d ) were formed by reactions of 1 a – 3 a {[(Cp*Ir)₂(pyrazine)Cl₂] ( 1 a ), [(Cp*Ir)₂(bpy)Cl₂] ( 2 a ), and [(Cp*Ir)₂(bpe)Cl₂] ( 3 a )} with malonic acid, fumaric acid, or H₂ADB (azobenzene‐4,4′‐chcarboxylic acid), respectively, under mild conditions. The metallamacrocycles were directly self‐assembled by activation of C? H bonds from dicarboxylic acids. Interestingly, after exposure to UV/Vis light, 3 c was converted to [2+2] cycloaddition complex 4 . The molecular structures of 2 b , 1 c , 1 d , and 4 were characterized by single‐crystal x‐ray crystallography. Nanosized tubular channels, which may play important roles for their stability, were also observed in 1 c , 1 d , and 4 . All complexes were well characterized by ¹H NMR and IR spectroscopy, as well as elemental analysis.     

Synthesis,Crystal Structure,Hydrogen Bonding,and Thermal Behavior of a Three‐Dimensional CuII‐benzene‐1,2,4,5‐tetracarboxylate Templated by 1,9‐Diaminononane

Triclinic single crystals of Cu₄(H₃N–(CH₂)₉–NH₃)(OH)₂[C₆H₂(COO)₄]₂ · 5H₂O were prepared in aqueous solution at 80 °C in the presence of 1,9‐diaminononane. Space group P$\bar{1}$ (no. 2) with a = 1057.5(2), b = 1166.0(2), c = 1576.7(2) pm, α = 106.080(10)°, β = 90.73(2)° and γ = 94.050(10)°. The four crystallographic independent Cu²⁺ ions are surrounded by five oxygen atoms each with Cu–O distances between 191.4(3) and 231.7(4) pm. The connection between the Cu²⁺ coordination polyhedra and the [C₆H₂(COO)₄]^4– anions yields three‐dimensional framework with negative excess charge and wide centrosymmetric channel‐like voids. These voids extend parallel to [001] with the diagonal of the nearly rectangular cross‐section of approximately 900 pm. The channels of the framework accommodate [H₃N–(CH₂)₉–NH₃]²⁺ cations and water molecules, which are not connected to Cu²⁺. The nonane‐1,9‐diammonium cations adopt a partial gauche conformation. Thermoanalytical measurements in air show a loss of water of crystallization starting at 90 °C and finishing at approx. 170 °C. The dehydrated compound is stable up to 260 °C followed by an exothermic decomposition yielding copper oxide.     

Crystalline Radicals Derived from Classical N‐Heterocyclic Carbenes

One‐electron reduction of C2‐arylated 1,3‐imidazoli(ni)um salts (IPr^Ar)Br (Ar=Ph, 3 a ; 4‐DMP, 3 b ; 4‐DMP=4‐Me₂NC₆H₄) and (SIPr^Ar)I (Ar=Ph, 4 a ; 4‐Tol, 4 b ) derived from classical NHCs (IPr=:C{N(2,6‐iPr₂C₆H₃)}₂CHCH, 1 ; SIPr=:C{N(2,6‐iPr₂C₆H₃)}₂CH₂CH₂, 2 ) gave radicals [(IPr^Ar)]^. (Ar=Ph, 5 a ; 4‐DMP, 5 b ) and [(SIPr^Ar)]^. (Ar=Ph, 6 a ; 4‐Tol, 6 b ). Each of 5 a , b and 6 a , b exhibited a doublet EPR signal, a characteristic of monoradical species. The first solid‐state characterization of NHC‐derived carbon‐centered radicals 6 a , b by single‐crystal X‐ray diffraction is reported. DFT calculations indicate that the unpaired electron is mainly located at the original carbene carbon atom and stabilized by partial delocalization over the adjacent aryl group.     

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.