Polysulfonylamine. VII. Aliphatische Trisulfonylamine

Polysulfonyl Amines. VII. Aliphatic Trisulfonyl Amines The compounds N(SO₂R¹)₂(SO₂R²) with R¹ = R² = CH₃ ( 2a ), R¹ = R² = C₂H₅ ( 2b ) and R¹ = CH₃, R² = C₂H₅ ( 2c ) are prepared by cleavage of aminostannanes (CH₃)₃SnN(SO₂R¹)₂ with sulfonyl chlorides R²SO₂Cl. A simple synthesis of 2a from AgN(SO₂CH₃)₂ and CH₃SO₂Cl is described. From the vibrational spectra of 2a , evidence is obtained for a planar NS₃ group in this compound. X-ray structure determinations of 2b and HN(SO₂C₂H₅)₂ ( 3 ) are reported. In 2b , the NS₃ group is approximately planar (S? N? S bond angles 119.0 ± 0.6°, sum of bond angles at N 356.9°); the S? N bond lengths of ca. 173 pm indicate a bond order of 1. In compound 3 , the nitrogen atom has a planar coordination (S? N? S angle 125.3°, sum of bond angles at N 359.3°), the S? N bond lengths of ca. 165 pm correlate with a bond order of 1.3? 1.4.     

A Design Strategy for Single‐Stranded Helicates using Pyridine‐Hydrazone Ligands and PbII

The reactions of py‐hz ligands ( L1–L5 ) with Pb(CF₃SO₃)₂?H₂O resulted in some rare examples of discrete single‐stranded helical Pb^II complexes. L1 and L2 formed non‐helical mononuclear complexes [Pb L1 (CF₃SO₃)₂]?CHCl₃ and Pb L2 (CF₃SO₃)₂][Pb L2 CF₃SO₃]CF₃SO₃?CH₃CN, which reflected the high coordination number and effective saturation of Pb^II by the ligands. The reaction of L3 with Pb^II resulted in a dinuclear meso‐helicate [Pb₂ L3 (CF₃SO₃)₂Br]CF₃SO₃?CH₃CN with a stereochemically‐active lone pair on Pb^II. L4 directed single‐stranded helicates with Pb^II, including [Pb₂ L4 (CF₃SO₃)₃]CF₃SO₃?CH₃CN and [Pb₂ L4 CF₃SO₃(CH₃OH)₂](CF₃SO₃)₃?2 CH₃OH?2 H₂O. The acryloyl‐modified py‐hz ligand L5 formed helical and non‐helical complexes with Pb^II, including a trinuclear Pb^II complex [Pb₃ L5 (CF₃SO₃)₅]CF₃SO₃?3CH₃CN?Et₂O. The high denticity of the long‐stranded py‐hz ligands L4 and L5 was essential to the formation of single‐stranded helicates with Pb^II.     

Polysulfonylamine. XLVI Molekülkomplexe von Di(organosulfonyl)aminen mit Dimethylsulfoxid und Triphenylphosphinoxid. Röntgenstrukturanalyse von Di(4-fluorbenzolsulfonyl)amin-Dimethylsulfoxid(2/1)

Polysulfonyl Amines. XLVI. Molecular Adducts of Di(organosulfonyl)amines with Dimethyl Sulfoxide and Triphenylphosphine Oxide. X-Ray Structure Determination of Di(4-fluorobenzenesulfonyl)amine-Dimethyl Sulfoxide(2/1) From equimolar solutions of the respective components in CH₂Cl₂/petroleum ether, the following crystalline addition compounds were obtained: (X? C₆H₄SO₂)₂NH …? OS(CH₃)₂, where X = H, 4? CH₃, 4? Cl, 4? Br, 4? I, 4? NO₂ or 3? NO₂; [(4? F? C₆H₄SO₂)₂NH]₂ · (OS(CH)₃)₂ ( 8 ); (4? I? C₆H₄SO₂)₂NH · OP(C₆H₅)₃. A (2/1) complex of (4? F? C₆H₄SO₂)₂NH with OP(C₆H₅)₃ could not be isolated. The solid-state structure of the (2/1) compound 8 is compared with the known structure of the (1/1) complex (CH₃SO₂)₂NH · OS(CH₃)₂. The crystallographic data for 8 at ?95°C are: monoclinic, space group C2/c, a = 2 369.9(13), b = 1 006.8(4), c = 2 772.6(13) pm, β = 110.71(4)°, U = 6.187 nm³, Z = 8. Two N? H …? O hydrogen bonds with N …? O 275 and 280 pm connect the disulfonylamine molecules with the dimethyl sulfoxide molecule. The O atom of the latter has a trigonal-planar environment consisting of the S atom and the two hydrogen bond H atoms.     

Organotin(IV) complexes of dibasic tridentate Schiff bases containing ONO donor atoms

Organotin(IV) Schiff base complexes of the type (L)SnR₂ [where R?CH₃, C₆H₅ or CH₂CH₂CO₂ CH₃], (LH)Sn(C₆H₅)₃ and (L)SnCl(CH₂CH₂CO₂ CH₃) [where LH₂?2-N-salicylideneimino-2-methyl-1-propanol, derived from the condensation of salicylaldehyde and 2-amino-2-methyl-1-propanol] have been prepared and characterized on the basis of their elemental analyses, IR, ¹H, ¹³C and ¹¹⁹Sn NMR studies. In these mononuclear complexes the Schiff base acts either as a dianionic tridentate or as a monobasic bidentate moiety by coordinating through an alkoxy group, an azomethine nitrogen and a phenoxide ion to tin. Sulphur dioxide inserts in the tin–methyl/–phenyl bond in the above Schiff base complexes to give tin–O–sulphinates of formulae (L)RSn(SO₂R) and (LH)(C₆H₅)₂Sn(SO₂C₆H₅).     

Koordination und Reaktivität von Sulfinylimiden RNSO in Cyclopentadienyldicarbonylmangan‐Komplexen

Coordination and Reactivity of Sulfinylimides RNSO in Cyclopentadienyldicarbonylmanganese Complexes The coordination behaviour of sulfinylimides RNSO (R = SiMe₃, Ph) towards CpMn(CO)₃ (Cp = C₅H₅, C₅H₄CH₃) has been studied. Under total exclusion of water the substitution products CpMn(CO)₂{S(O)NR} ( 2 a , b , 2 ′ a , b ) with μ¹‐S‐linkage are formed. In the presence of water, however, the SO₂ complexes 3 , 3 ′ as iminofree hydrolysis products are obtained. There are only spectroscopic indications for the directed hydrolytic conversion of the silyl derivatives 2 a , 2 ′ a into the unstable HNSO complexes 4 , 4 ′ by cleavage of the Si–N‐bond and retention of the cumulene moiety. The molecular structures of π‐C₅H₅Mn(CO)₂{S(O)NSiMe₃} ( 2 a ) and π‐C₅H₄CH₃Mn(CO)₂SO₂ ( 3 ′) were elucidated by single crystal X‐ray analyses.     

Thermal behavior of some compounds of methanesulfonic acid with transition metals

The following compounds of methanesulfonic acid, CH₃SO₃H, have been prepared: Cu(CH₃SO₃)₂ · 4 H₂O; Zn(CH₃SO₃)₂ · 4 H₂O; Mn(CH₃SO₃)₂ · 2 H₂O; Cd(CH₃SO₃)₂ · 2 H₂O and Ag(CH₃SO₃). Their thermal behavior has been studied using TG and DTA, together with X-ray analysis of the solid products formed during the heating. The water of hydration is evolved in one step (Mn, Cd) or in two step (Cu, Zn). The intermediate hydrates and the anhydrous salts are crystallized. The anhydrous Zn, Ag and Cd compounds melt, the anhydrous Cd salt undergoing a polymorphic transition before melting. They then begin to decompose in the temperature range 325–440°C. Under an inert atmosphere, the decomposition yields well-crystallized residues of various composition: Cu + Cu₂S; Ag + Ag₂S (the sulfides being in very minute amounts); MnS; CdS; ZnO + ZnS.     

Komplexchemie reaktiver organischer Verbindungen. XLV. Metallorganische Methandiazo – Komplexe: Protonierung und Cycloaddition

Complex Chemistry of Reactive Organic Compounds. XLV. Organometallic Methanediazo Complexes: Protonation and Cycloaddition The reactions of the methanediazo tungsten complex (η⁵-C₅H₅)W(CO)₂(N₂CH₃) ( 1 ) with protic acids are strongly governed by solvent effects: while trifluoromethylsulfonic acid induces clean protonation with formation of the ionic derivative [(η⁵-C₅H₅)W(CO)₂(HN₂CH₃)]+CF₃SO₃? ( 3 ) when diethylether is used as a solvent, compound 4 is formed in the presence of acetonitril which latter solvent has good coordination capabilities itself. Compound 4 originates from a novel type of cycloaddition reaction in which the protonated species of composition [(η⁵-C₅H₅)W(CO)(CH₃CN)(HN₂-CH₃)]+CF₃SO₃? is involved. Complete elimination of the nitrogeneous ligand ensemble with concomitant formation of the halogen complex (η⁵-C₅H₅)W(CO)₂Br₃ ( 5 ) occurs upon treatment of 1 with hydrogen bromide.     

Oxidation of γ-stannyl sulfides by monochloramine CB and hydrogen peroxide

The first γ-trimethylstannyl sulfimide, Me³Sn(CH₂)₃S(=NSO₂Ar)C₅H₁₁-n, was synthesized by oxidative imination of Me₃Sn(CH₂)₃SC₅H₁₁-n with ArSO₂(Na)Cl (Ar=C₆H₄Cl-4). Oxidation of γ-trimethylstannyl sulfimide by an alkaline solution of H₂O₂ gave γ-trimethylstannyl sulfoximide, Me₃Sn(CH₂)₃S(O)(=NSO₂Ar)C₅H₁₁-n, and γ-trimethylstannyl sulfone, Me₃Sn(CH₂)₃SO₂C₅H₁₁-n, the latter compound resulting from hydrolysis of the arylsulfimide group. Oxidation of stannyl sulfide by hydrogen peroxide yielded γ-trimethylstannyl sulfoxide, Me₃Sn(CH₂)₃S(O)C₅H₁₁-n (under mild conditions) or γ-trimethylstannyl sulfone (under more severe conditions). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 371–374, February, 1997.     

Metallkomplexe mit biologisch wichtigen Liganden. CLVII [1] Halbsandwich‐Komplexe mit Isocyanoacetylaminosäureestern und Isocyanoacetyldi‐ und tripeptidestern („Isocyano‐Peptide”︁)

Metal Complexes of Biologically Important Ligands, CLVII [1] Halfsandwich Complexes of Isocyanoacetylamino acid esters and of Isocyanoacetyldi‐ and tripeptide esters (?Isocyanopeptides”?) N‐Isocyanoacetyl‐amino acid esters CNCH₂C(O) NHCH(R)CO₂CH₃ (R = CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, CH₂C₆H₅) and N‐isocyanoacetyl‐di‐ and tripeptide esters CNCH₂C(O)NHCH(R¹)C(O)NHCH(R²)CO₂C₂H₅ and CNCH₂C(O)NHCH(R¹)C(O)NHCH (R²)C(O)NHCH(R³)CO₂CH₃ (R¹ = R² = R³ = CH₂C₆H₅, R² = H, CH₂C₆H₅) are available by condensation of potassium isocyanoacetate with amino acid esters or peptide esters. These isocyanides form with chloro‐bridged complexes [(arene)M(Cl)(μ‐Cl)]₂ (arene = Cp*, p‐cymene, M = Ir, Rh, Ru) in the presence of Ag[BF₄] or Ag[CF₃SO₃] the cationic halfsandwich complexes [(arene)M(isocyanide)₃]⁺X^? (X = BF₄, CF₃SO₃).     

Reactions of the nitrate radical with a series of reduced organic sulphur compounds in air

A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO₃, and the reduced organic sulphur compounds CH₃CH₂SH, (CH₃CH₂)₂S, (CH₃CH₂)₂S₂, and CH₃CH₂SCH₃ in air. The products CH₃CH₂SO₃H, SO₂, H₂SO₄, CH₃CHO, and CH₃CH₂ONO₂ were identified and quantified in the reactions of the first three compounds, CH₃CH₂SH, (CH₃CH₂)₂S, and (CH₃CH₂)₂S₂. The reaction products were CH₃CH₂SO₃H, CH₃SO₃H, SO₂, H₂SO₄, CH₃CHO, and CH₂O in the reaction of CH₃CH₂SCH₃. On the basis of identified reaction products and intermediates observed in the infrared spectra, mechanisms are proposed for the reactions between the NO₃ radical and the four reduced organic sulphur compounds. The results of this study, together with those from previous experiments performed in this laboratory on CH₃SCH₃, CH₃SH, and CH₃SSCH₃ lead to the conclusion that all these species, in the reaction with the NO₃ radical, follow a similar degradation mechanism producing SO₂, H₂SO₄, R? SO₃H, R? CHO, and R? CH₂ONO₂, as the main reaction products. The inital step of the reaction of NO₃ with R? S? R and R? S? H type (R = CH₃, CH₂CH₃) reduced organic sulphur compounds was found to be H-atom abstraction, probably after the formation of an initial adduct. For the reaction between NO₃ and R? S? S? R type compounds, evidence for an addition-decomposition reaction, as the initial steps, was obtained. R? S·, R? S(O)·, and R? S(O)₂· appear to be formed as intermediates in all the reactions. © John Wiley & Sons, Inc.     

Preparation and configurational isomerism of ditertiary stibine sulfides, (C6H5)(CH3)(S)SbCH2Sb(CH3)(C6H5) and [(C6H5)(CH3)(S)Sb]2(CH2)3

Asymmetric ditertiary stibine sulfides (C₆H₅)(CH₃)(S)SbCH₂Sb(CH₃)(C₆H₅) and [(C₆H₅)(CH₃)(S)Sb]₂(CH₂)₃ have been prepared. It was found that they exist as only one of two possible diastereomers in the crystalline state. However, isomerization to the other form takes place in solution, resulting in an equilibrium mixture. A possibility of configurational lability of tertiary stibine sulfide was suggested for the first time.     

Synthesis and reactions of some sulfur ylide complexes of palladium

The iodo-bridged sulfur ylide complex [Pd(μ-I)((CH₂)₂(SO)(CH₃))]₂ (1) when treated with dithiolates, acetylacetone and various Lewis bases gave [Pd((CH₂)₂(SO)(CH₃))(S ∼ S)] (S ∼ S = S₂CN(C₂H₅)₂, S₂COC₂H₅ and S₂P(OC₂H₅)₂), [Pd((CH₂)₂(SO)(CH₃))(acac)] (acac = acetylacetonate) and [PdI((CH₂)₂(SO)(CH₃))(base)]a (base = PPh₃, (P(OMe)₃, P(OPh)₃ and C₅H₅N). In the presence of a phase transfer catalyst (PTC). The reactions rates and yields were greatly increased. Reaction of several related sulfur ylide complexes with I₂, HI or aqueous NaOH gave 1. The single crystal structure of [Pd((CH₂)₂(SO)(CH₃))₂] was determined (orthorhombic, Pbcn, a 13.379(2), b 8.081(1), c 9.048(2) Å, V 978.2 ų, Z = 4). The compound has a rather long PdCH₂ bond (2.096(1) Å, mean).     

Synthese und Röntgenstrukturanalyse von S4N4-Derivaten mit drei- und vierfach koordinierten Schwefelatomen

CF₃SO₂N?SCl₂ reagiert mit (CH₃)₂S[NSi(CH₃)₃]₂, (C₄H₈)S[NSi(CH₃)₃]₂ oder (C₅H₁₀)S[NSi(CH₃)₃]₂ unter Trimethylchlorsilanabspaltung zu den achtgliedrigen S₄N₄-Derivaten S₄N₄(NSO₂CF₃)₂(CH₃)₄ 3 , S₄N₄(NSO₂CF₃)₂(C₄H₈)₂ 4a und S₄N₄(NSO₂CF₃)₂(C₅H_{1 0})₂ 4b . In den achtgliedrigen SN-Ringen haben die Schwefelatome die Koordinationszahl 3 und 4. Die Röntgenstrukturanalyse von 4a ergab eine Sessel-Konformation. 4a kristallisiert orthorhombisch in der Raumgruppe Pna2₁ mit a = 17,641(4), b = 6,406(2), c = 19,130(4) Å, d_x = 1,815 g cm^?3 und Z = 4. Die mittleren S? N-Abstände betragen an den vierfach koordinierten Schwefelatomen 1,597 Å und an den Schwefelatomen mit der Koordinationszahl 3 1,650 Å. CF₃SO₂N? SCl₂ reagiert mit trimethylzinnhaltigen S? N-Verbindungen zum bekannten CF₃SO₂N[Sn(CH₃)₃]S(CH₃)NSO₂CF₃ und Dimethylzinndichlorid. Synthesis and X-Ray Structure Analysis of S₄N₄-Derivatives with Threefold and Fourfold Coordinated Sulfur Atoms CF₃SO₂N?SCl₂ reacts with (CH₃)₂S[NSi(CH₃)₃]₂, (C₄H₈)S[NSi(CH₃)₃]₂ or (C₅H₁₀S[NSi(CH₃)₂]₂ under elimination of (CH₃)₃SiCl to yield the eight-membered S₄N₄ derivatives S₄N₄?NSO₂CF₃)₂(CH₃)₄, 3 , S₄N₄(NSO₂CF₃)₂(C₄H₈)₂ 4a und S₄N₄(NSO₂CF₃)₂(C₅H_{1 0})₂ 4b . In the eight-membered SN-rings the sulfur atoms have the coordination number 3 and 4. The X-ray structure analysis of 4a revealed a chair conformation. 4a crystallizes in the orthorhombic space group Pna2₁ with a = 17.641(4), b = 6.406(2), c = 19.130(4) Å, d_x = 1.815 g cm^?3, and Z = 4. The average S? N distance was found to be 1.597 Å at fourfold coordinated sulfur atoms and 1.650 Å at sulfur with coordination number 3. CF₃SO₂N=SCl₂ reacts with trimethyl tin-containing S? N compounds to the known CF₃SO₂N[Sn(CH₃)₃]S(CH₃)NSO₂CF₃ and dimethyl tin dichloride.     

Kinetic studies of the reactions of the carbene complex W(CO)5[C(SCH3)2] with phosphines to form phosphorane complexes W(CO)5[(CH3S)2C-PR3] and the synthesis of some cyclic phosphorane complexes

The dithiocarbene complex W(CO)₅[C(SCH₃)₂ reacts with tertiary phosphines, PPh₂CH₃, PPh(CH₃)₂, P(C₂H₅)₃ and P(OCH₃)₃ to form the phosphorane complexes W(CO)₅[CH₃S)₂C-PR₃] and with HPPh₂ to form the phosphine complex W(CO)₅[PPh₂[CH(SCH₃)₂]. Kinetic studies of both types of reactions show that their rates are first order each in W(CO)₅[C(SCH₃)₂] and in the phosphorus ligand. A mechanism involving rate determining phosphorus attack at the carbene carbon followed by rapid rearrangement to the product is consistent with this rate law. Rate constants for the reactions increase with increasing nucleophilicities of the phosphines: P(OCH₃)₃ < PPh₂H < PPh₂C_H3 ? PPh(CH₃)₂ < P(C₂H₅)₃. The ΔH values decrease (P(OCH₃)₃ > PPh₂H > PPh₂(CH₃) > PPh(CH₃)₂ > P(C₂H₅)₃) as the nucleophilicities of the phosphines increase. The ΔS values (≈-30 e.u.) remain essentially constant for all the reactions. The cyclic dithiorcarbenes W(CO)₅[CS(CH₂)_nS], wheren- 3 or 4, react with PPh₂(CH₃) to form the cyclic phosphorane complexes, W(CO)₅[S(CH₂)_nSC-PPh₂(CH₃)]. The 6- and 7- membered cyclic dithiocarbenes also react with PPh₂H to form the phosphine complexes, W(CO)₅ {PPh₂- [CS(CH₂)_nS(H)]}.     

Aminorhenium carbon dioxide complexes: formal oxidation of a carbon monoxide ligand with peroxy-acids or bromine/hydroxide

The electron-rich aminorhenium complexes η⁵:η¹-C₅H₄CH₂CH₂NR(CH₃)Re(CO)₂ (3a-d; R=methyl, benzyl, n-butyl, n-butyl-OH) are easily oxidized with peroxy-acids to give the corresponding η²-CO₂ complexes η⁵: η¹- C₅H₄CH₂CH₂NR(CH₃)Re(CO)(η²-CO₂) (4a-d) in excellent yield. The resultant η²-CO₂ complex is predominantly the anti-isomer. The structures of η²-CO₂ complex η⁵:η¹-C₅H₄CH₂CH₂N(CH₃)(n- C₄H₈OH)Re(CO)(η²-CO₂) (4d-anti) and the corresponding CO complex 3d have been confirmed by X-ray crystallography. The η²-CO₂ complexes 4a-4d are stable at ambient temperature under air. In addition to peroxy-acid oxidation, bromination of the aminorhenium dicarbonyl complexes followed by base treatment also provided the corresponding η²-CO₂ complexes. The reaction mechanism for the formation of CO₂ complex from the corresponding dicarbonyl is discussed briefly.     

Homogeneous Catalytic Hydrogenation of Amides to Amines

Hydrogenation of amides in the presence of [Ru(acac)₃] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)₃], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH₂(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ¹O)₂(H₂O)(triphos)], [Ru(OAc‐κ²O,O′)(CH₃SO₃‐κ¹O)(triphos)], [Ru(CH₃SO₃‐κ¹O)₂(H₂O)(triphos)] and [Ru₂(μ‐CH₃SO₃)₃(triphos)₂][CH₃SO₃], whereas other complexes, such as [Ru(OAc‐κ¹O)(OAc‐κ²O,O′)(triphos)], [Ru(CH₃SO₃‐κ¹O)(CH₃SO₃‐κ²O,O′)(triphos)], H[Ru(CH₃SO₃‐κ¹O)₃(triphos)], [RuH(CH₃SO₃‐κ¹O)(CO)(triphos)] and [RuH(CH₃SO₃‐κ²O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.     

Mass spectra of 5-fluorouracil derivatives. N-1-substituted sulfonyl derivatives

The electron impact mass spectra of 1-sulfonyl substituted derivatives of 5-fluorouracil were investigated. The substituents were CH₃SO₂ (compound I), CH₃(CH₂)₃SO₂ (II), C₆H₅SO₂ (III) and p-CH₃C₆H₄SO₂ (IV).     

Reaction of hydrogen atoms with dimethyldisulfide

Hydrogen atoms, generated by the mercury (³P₁) sensitization of H₂, were allowed to react with dimethyldisulfide in the temperature range of 25–155°C. The only retrievable product is methanethiol, formed in the primary metathetical reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H} + {\rm CH}_3 {\rm SSCH}_3 {\rm CH}_3 {\rm SH} + {\rm CH}_3 {\rm S} $\end{document}. The intermediacy of thiyl radicals was clearly demonstrated in experiments carried out in the presence of ethylene where one of the major products detected was ethyl methyl sulfide, formed via CH₃S + C₂H₅ → CH₃SC₂H₅. The major fate of the CH₃S radical is recombination and disproportionation, and the yield of methanethiol formed via disproportionation contributes less than 5% to the total thiol yield. The rate coefficient of step 1, from competition with the reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H} + {\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm C}_{\rm 2} {\rm H}_5 $\end{document}, is k₁ = (5.7 ± 1.2) × 10¹² exp[? (100 ± 100)/RT] cm³/mol sec.     

一系列由柔性N,N'-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)4](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}_n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)2·9H₂O}_n (5),其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构,配合物5为二维层状结构,其中金属离子由质子化的bpma配体桥连。值得注意的是,采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构,配合物3和4为螺旋链结构,配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

一系列由柔性N,N'-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)₄](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)₂·9H₂O}_n (5), 其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构, 配合物5为二维层状结构, 其中金属离子由质子化的bpma配体桥连。值得注意的是, 采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构, 配合物3和4为螺旋链结构, 配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。