Biocidal Organotin Compounds. Part 2. Synthesis,Characterization and Biocidal Properties of Triorganotin(IV) Hydantoic Acid Derivatives and the Crystal Structures of Triphenyltin and Tricyclohexyltin Hydantoates

The preparation and spectroscopic (¹H NMR, UV and IR) characterization of three R₃Sn(O₂CCH₂N(H)C(O)NH₂) [R=Ph, c-Hex (cyclohexyl) or n-Bu] compounds are reported. A different mode of coordination is indicated for the hydantoate ligand in the R=Ph compound compared with the R=c-Hex and R=n-Bu compounds, as confirmed by a crystallographic analysis. The structure of [Ph₃Sn(O₂CCH₂N(H)C(O)NH₂)] is polymeric owing to the presence of bridging hydantoate ligands such that each ligand coordinates one tin atom, via one of the carboxylate oxygen atoms, and a symmetry-related tin atom via the carbonyl group at the other end of the molecule. The structure features distorted trigonal-bipyramidal tin atom geometries with a trans -R₃SnO₂ motif. The structure of [c-Hex₃Sn(O₂CCH₂N(H)- C(O)NH₂)], by contrast, is monomeric, distorted tetrahedral, as the carboxylate group is monodentate and there are no additional tin–ligand interactions. The structures are each stabilized by a number of intermolecular hydrogen bonds. Fungitoxicity and phytotoxicity studies indicate that the R=n-Bu derivative is the more active compound.     

Metal complexes of hybrid oxygen-arsenic ligands. Part V. A study of the products fromo-R2AsC6H4CO2M and CrO3 (M = H)/trans-[CrCl2(OH2)4]Cl · 2H2O (M = Na) in acetone

Summary A change of the reported medium of reaction oftrans- [CrCl₂(OH₂)₄]Cl · 2H₂O witho-R₂AsC₆H₄CO₂M (M = Na), from 95% ethanol to acetone, results in the change of an hydroxo — to an oxo — group (R = Ph), in the number of water molecules (R = Et or C₆H₁₁) and/or of ligand molecules (R =p-tolyl) in chromium(III)-arsine complexes. However, for R = Me, the same complex is obtained in each case. I.r. spectral data of these complexes favour the chelation of the carboxylate ion and non-coordination of arsenic(III) except for CrO(o-Ph₂AsC₆H₄CO₂) · 2.5 H₂O in which arsenic(III) of the monotertiary arsine group appears to coordinate to chromium(III). This would seem to be the first example of this type. On the other hand, the reaction of CrO₃ witho-R₂As- C₆H₄CO₂M (M = H) in 14.5 molar ratio in acetone yields only one type of complex,viz., [Cr₃O₃(o-R₂As(O)C₆H₄-CO₂)₂(o-R₂AsC₆H₄CO₂)(H₂O)₆] · n H₂O (n = 2, R = Me, C₆H₁₁ or Ph; n = O, R = Et). The arsine oxide molecules appear to chelate through As = 0 and the carboxylate oxygens while the arsine ligand binds only through the carboxylate oxygens leaving arsenic(III) uncoordinated as reported for the complexes obtained from the same reactants in 95% ethanol.     

Structural chemistry of organotin carboxylates: I. The crystal structure of di-n-butylbis(thiophenoxyacetato)tin(IV): nBu2Sn(O2CCH2SC6H5)2

A crystal structure study of ⁿBu₂Sn(O₂CCH₂SC₆H₅)₂ reveals the compound to be monomeric with the tin atom situated on a crystallographic 2-fold axis in a skew-trapezoidal bipyramidal geometry. The basal plane is defined by two asymmetrically chelating carboxylate groups; SnO 2.134(4) and 2.559(5) Å and the ⁿBuSnⁿBu angle is 140.7(2)°. The sulphur atoms do not participate in any significant interactions to the tin atom. Crystals are monoclinic with space group C2 and unit cell dimensions a 18.668(6), b 15.761(6), c 5.106(5) Å, β 117.55(5)°; Z = 2. The structure was refined by a full-matrix least-squares procedure to final R = 0.034 and R_w = 0.033 for 1294 reflections with I ≥ 2.5σ(I).     

Consequences of acceptor effects on the polarization of oxo and imine bonds in acyl and R-CO-COOH compounds: Part III. Acid-base equilibria antecedent to the reduction of α-ketoacids at the DME

It is usually assumed that in α-ketoacids (R-CO-COO?), when the pH increases, the antecedent protonation occurs at the carboxylate group.A comparison of the cathode half-wave potentials and the ratio ΔE1/2/ΔpH as well as the determination of Taft's polar substituents δCOO?* and δCOOH* lead us to postulate that, in neutral media, the recorded recombination current corresponds to antecedent protonation of the carbonyl function. The antecedent protonation of the carboxylate group only occurs in a more acid medium (1<pH<5).The hydrate is not reducible because its protonation, followed by hydration, only occurs at the electrode at pH lower than 1.     

(−)-isovaline: confirmation of its D-(=R)-configuration by X-ray analysis of its N-chloroacetyl derivative

The N-chloroacetyl derivatives of (?)-isovaline 1 crystallizes in space group P2₁ with Z = 4 and a = 10.675(6), b = 7.698(4), c = 11.739(2) Å and β = 97.32(4)°. The structure was solved by the heavy atom method and refined to R = 0.0718 and R_G = 0.0991 with 1890 independent reflexions (F₀ > 0). The absolute configuration of 1 was determined as R by application of the Hamilton test with two data sets (CuK_α and MoK_α-radiation). There are two independent molecules 1 showing flat backbone confirmations, which include weak intramolecular bifurcated hydrogen bonds. Strong intermolecular hydrogen bonds determine the crystal packing, in which antiparallel chains of single molecules run along [010]. The (R)-assignment is in agreement with the order of elution (d before l) of enantiomers of N-trifluoroacetyl-dl-isovaline-n-propyl ester on glass capillaries coated with the chiral phase N-propionyl-l-valine-t-butylamide-polysiloxane.     

Structure of palladium(I) carbonylcarboxylate clusters [Pd<Subscript>2</Subscript>(CO)<Subscript>2</Subscript>(RCOO)<Subscript>2</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> in solution: NMR and IR study

The structures of palladium carbonylcarboxylate clusters [Pd₂(CO)₂(RCOO)₂] _n (n = 2, R = CH₃, CH₂Cl, CF₃, n = 3, R = CMe₃, CHMe₂, n-C₅H₁₁) are studied in benzene and tetrahydrofuran solutions by IR and ¹H and ¹³C NMR spectroscopy. The clusters in the solid state have a planar cyclic metal framework with pairs of the carbonyl and carboxylate ligands alternately coordinated on its sides. In solutions, compounds under consideration contain one-type carbonyl ligands and one-type carboxylate ligands; their structures are similar to thaso in the solid state.     

In vitro antitumor and antibacterial assay of organotin(IV) complexes of 2,3-methylenedioxybenzoic acid; X-ray crystal structure of [(C2H5)2Sn(C8H5O4)2]

New organotin(IV) compounds containing the carboxylate ligand 2,3-methylenedioxybenzoic acid (HL) have been synthesized with the general formula R₂SnL₂ (R = Me, Et, n-Bu, Ph and n-Oct) and R₃SnL (R = n-Bu). All compounds have been studied in the solution state by multinuclear NMR (¹H, ¹³C and ¹¹⁹Sn) by using the non-coordinating solvent and also in solid sate by FTIR, mass spectrometry and X-ray crystallography. Spectroscopic data have shown that methylenedioxy moiety does not coordinate with tin atom and the coordination site is actually -COO group, as is proved by X-ray structure determination. The solid state structure of compound (2) has been determined by X-ray crystallography which shows that the complex (2) has distorted octahedral geometry. These complexes have been evaluated in vitro against crown gall tumor and antibacterial activity. Interesting results were noticed during the bio-activity screenings, which proved their in vitro biological potential and possible use as drugs.     

Crystal and molecular structure of the volatile mixed-ligand complex Zn(S2CN(i-C4H9)2)2Phen

The crystal and molecular structure of the mixed-ligand complex Zn(S₂CN(i-C₄H₉)₂)₂Phen was determined by single-crystal X-ray diffractometry (Syntex P2₁ diffractometer, CuK_α radiation, 1738 F(hkl),R = 0.036). The crystals are triclinic, a =18.564(4), b =10.487(1), c =17.505(4) å, α = 84.04(2), Β =94.88(2), γ =90.87(2)?;V =3377(1) å ³, Z = 4, d_calc = 1.287 g/cm³, space group C-1. The structure consists of monomeric molecules in which the zinc atom has a distorted octahedral environment (4S+2N).     

Cobalt(II) complex with pyridyl nitronyl nitroxide radical: Synthesis, crystal structure, and magnetic property of [Co(PyNIT)2(PhCOO)2(H2O)2]

A new cobalt coordination compound with nitronyl nitroxide and benzonate, Co(PyNIT)₂(PhCOO)₂(H₂O)₂, where PyNIT = 2-(p-pyridyl)-4,4??,5,5??-tetramethylimidazoline-1-oxyl-3-oxide, was synthesized and its X-ray diffraction analysis was carried out. The crystals were triclinic: a = 6.7749(4), b = 11.3472(7), c = 12.9066(8) ?, ?? = 87.906(1)°, ?? = 88.631(1)°, ?? = 79.080(1)°, V = 973.45(10) ?³, space group P $ \bar 1 $ , Z = 1, ??_calcd = 1.375 mg/m³, R = 0.0316. The environment of the cobalt atom is distorted octahedral formed by two oxygen atoms of two carboxylate groups of benzoate, two oxygen atoms of waters and two nitrogen atoms from two pyridyl nitronyl nitroxide molecules.     

Reactions of 1,4-diaza-3-methylbutadien-2-ylpalladium(II) derivatives with chloro-bridged rhodium(I) complexes

The reactions of the organometallic 1,4-diazabutadienes, RN=C(R′)C(Me)=NR″ [R = R″ = p-C₆H₄OMe, R′ = trans-PdCl(PPh₃)₂ (DAB); R = p-C₆H₄OMe, R″ = Me, R′ = trans-PdCl(PPh₃)₂ (DAB^I; R = R″ = p-C₆H₄OMe, R′ = Pd(dmtc)-(PPh₃), dmtc = dimethyldithiocarbamate (DAB^II); R = R″ = p-C₆H₄OMe, R′ = PdCl(diphos), diphos = 1,2-bis(diphenylphosphino)ethane (DAB^III)] with [RhCl(COD)]₂ (COD = 1,5-cyclooctadiene, Pd/Rh ratio = $\text{1}\text{2}$) depend on the nature of the ancillary ligands at the Pd atom in group R′. In the reactions with DAB and DAB^I transfer of one PPh₃ ligand from Pd to Rh occurs yielding [RhCl(COD)(PPh₃)] and the new binuclear complexes [Rh(COD) {RN=C(R?)-C(Me)=NR″}], in which the diazabutadiene moiety acts as a chelating bidentate ligand. Exchange of ligands between the two different metallic centers also occurs in the reaction with DAB^II. In this case, the migration of the bidentate dmtc anion yields [Rh(COD)Pdmtc] and [Rh(COD) {RN=C(R?)C(Me)=NR″}]. In contrast, the reaction with DAB^III leads to the ionic product [Rh(COD)- (DAB^III)][RhCl₂(COD)], with no transfer of ligands. The cationic complex [Rh(COD)(DAB^III)]⁺ can be isolated as the perchlorate salt from the same reaction (Pd/Rh ratio = 1/1) in the presence of an excess of NaClO₄. In all the binuclear complexes the coordinated 1,5-cyclooctadiene can be readily displaced by carbon monoxide to give the corresponding dicarbonyl derivatives. The reaction of [RhCl(CO)₂]₂ with DAB and/or DAB^I yields trinuclear complexes of the type [RhCl(CO)₂]₂(DAB), in which the diazabutadiene group acts as a bridging bidentate ligand. Some reactions of the organic diazabutadiene RN=C(Me)C(Me)=NR (R = p-C₆H₄OMe) are also reported for comparison.     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

Crystal and molecular structure of the monoclinic modification of Mn(S2CO-i-C3H7)2(2,2’-bipy)

The crystal and molecular structure of modification II of the Mn(S₂CO-i-C₃H₇)₂(2,2’-Bipy) complex was determined from X-ray diffraction data (“Syntex P2₁” diffractometer, CuK_α radiation, 1603 F(hkl), R = 0.0446). The crystals are monoclinic,a = 23350(3),b = 9.325(1),c = 22.030(2) å, Β = 106.98(1)?,V = 4587.7 å³, Z =8, d _calc = 1.394 g/cm³, space group C2/c. The structure consists of monomeric molecules in which the manganese atom has a distorted octahedral environment (4S + 2N). The orthorhombic and monoclinic modifications of the complex are compared with respect to the molecular geometry and packing.     

Crystal and molecular structure of the mixed-ligand complex Zn[S2CN(CH3)2]2Phen

The crystal and molecular structure of the mixed-ligand complex Zn[S₂CN(CH₃)₂]₂Phen is determined by single crystal X-ray diffractometry (CAD-4 diffractometer, MoK_α radiation, 3347 F(hkl), R = 0.0385). The crystals are monoclinic, a =13.340(3), b =13.827(3), c =24.698(5) å, Β =102.58(3)? V = 4446(2) å ³, Z = 8, d_calc = 1.452 g/cm³ , space group C2/c. The structure consists of monomeric molecules in which the zinc atom has a distorted octahedral environment (4S+2N). The molecular packing in the crystal involves dimers related by the 2 rotation axis and forming continuous chains along the c axis.     

X-ray diffraction study of the clathrate [MnPy4(NO3)2)]·2Py and complex [MnPy3(NO3)2] formed in the pyridine (Py)-manganese nitrate system

A clathrate compound [MnPy₄(NO₃)₂]·2Py was synthesized and studied by single-crystal X-ray diffraction analysis (KM-4 diffractometer, CuK_α,ω/2? scan mode,? _max=78°). The unit cell is base-centered orthorhombic, space group Ccca, a=12.097(4), b=15.197(4), c=17.213(4) Å, V=3164(2) ų, Z=4, R=0.072, for 632 reflections and 107 parameters in the least-squares analysis. The host molecule has 222 symmetry. Two monodentate nitrato groups and four pyridine ligands are coordinated to Mn(II) along the symmetry axes (the former via O). The pyridine guest molecules lie in the cavities of the crystal framework. For [MnPy₃(NO₃)₂)], only unit cell parameters were determined: a=12.467(5), b=9.514(2), c=16.383(5) Å,β=108.93(4), V=1838(1) ų space group C2/c or Cc (according to extinctions). The pyridine-manganese nitrate system is shown to be analogous to the previously investigated Co, Ni, Cu, Zn, and Cd systems.     

Chelatkomplexe LM/n von Übergangsmetallen mit Iminophosphin-säureamidato-Liganden R2P(NR′)2– (= L)

Chelate Complexes LM/n of Transition Metals with Phosphinoimidic Amidato Ligands R₂P(NR′)₂^– (= L) Reaction of LLi with metal halides or metal halide complexes affords chelate complexes LM/n (L = R₂P(NR′)₂^–; M = Cr⁺⁺⁺, Co⁺⁺, Ni⁺⁺, Zn⁺⁺). With the bulky ligand t-Bu₂P(NSiMe₃)₂^– and Ni(PPh₃)₂Cl₂ or Ni(dme)Br₂ (dme = dimethoxyethane) only halide bridged chelates [LNiHal]₂ (Hal = Cl, Br) containing tetrahedral chromophors NiN₂Hal₂ were obtained. Main objects of investigation were the bischelates L₂Ni 2 . 2 a (R = i-Pr, R′ = Me) and 2 c (R = Ph, R′ = Et) are planar, 2 b (R = i-Pr, R′ = Et) and 2 d–g (R, R′ = i-Pr, i-Pr; Ph, i-Pr; Et, SiMe₃; Ph, SiMe₃) tetrahedral. In solutions of 2 b and 2 c a conformational equilibrium planar (diamagnetic) tetrahedral (paramagnetic) exists that is shifted to the right with increasing temperature and is dominated by the tetrahedral ( 2 b ) or planar conformer ( 2 c ) at room temperature. As is the case with the isovalence electronic compounds [R₂P(S)NR′]₂Ni small substituents R′ apparently favour the planar state and in contrast to some complexes [R₂P(O)NR′]₂Ni no paramagnetic planar species 2 have yet been observed. These findings that are derived from the results of magnetic measurements and of UV/VIS as well as NMR spectroscopy are confirmed by crystal structure determinations: 2 a was found to be planar (orthorhombic; a = 3382.8(11), b = 1124.0(4), c = 8874(3); P2₁2₁2; Z = 6), and 2 g to be tetrahedral (monocline; a = 1268.4(2), b = 1806.8(2), c = 1971.6(2), P2₁/n; Z = 4). The bite angle NNiN of the chelate ligand in 2 a (ca. 77°) is similar to those in paramagnetic planar complexes [R₂P(O)NR′]₂Ni (NNiO 74–77°) and shows that a small chelate bite does not necessarily imply paramagnetism of planar Ni(II) complexes.     

Further study of estertin trichlorides,Cl3SnCH2CH2CO2R. Lewis acidity towards acetonitrile. Crystal structure of Cl3SnCH2CH2CO2Pr-i

Crystals of Cl₃SnCH₂CH₂CO₂Pri-i are orthorhombic, space group P2₁2₁2₁ with a 9.638(6), b 10.004(7) and c 12.848(8) Å. The tin atom is five-coordinate with two chlorines and carbon equatorial and the remaining chlorine and the carbonyl oxygen axial, in a distorted trigonal-bipyramidal arrangement: (SnCl)_ax 2.389(3), average (SnCl)_eq 2.320(2), SnC 2.142(9), SnO 2.337(5) Å. Apart from the equatorial chlorine and the terminal carbons in the isopropyl group, all non-hydrogen atoms are essentially coplanar. The molecule approaches C_2v symmetry although not constrained to do so by the crystallographic space group.In MeCN solution, the compounds Cl₃SnCH₂CH₂CO₂R (I, R = Me, Pr-i, C₆H₄X (X = p-MeO, H, p-Cl, o-MeO or C₆H₃Cl₂-2,4) form as equilibrium mixtures of 1/1 and 2/1 MeCN/I complexes; the chelate ring is broken in the 2/1 complexes. Equilibrium constants indicate that the strength of the intramolecular SnO coordination in I increases with the electron releasing ability of the R group.     

Umlagerung und Spaltung von α, β-Dioxopropionsäureestern in alkalischem Milieu. 28. Mitt. über Reduktone und Tricarbonylverbindungen [1]

The behaviour of α,β-dioxopropionic acid derivatives of the type R? CO? CO? COX (R = phenyl, p-substituted phenyls, CF₃, mesityl; X = OC₂H₅, NH₂) was investigated under benzilic acid rearrangement conditions. Nearly all compounds were cleaved by alkali to give the corresponding acids R? COOH and glyoxylic acid. Only the sterically hindered ethyl β-mesityl-α,β-dioxopropionate underwent rearrangement (after hydrolysis of the ester group); it was shown by ¹⁴C-labelling that the carboxylate group migrates to the β-carbonyl group.     

Reaction of MeO2C(H)C=C=C(H)CO2Me with Ru3(CO)12. New diruthenium complexes with bridging carboxylate-substituted allene ligands

The reaction of Ru₃(CO)₁₂ with MeO₂C(H)C=C=C(H)CO₂ Me has yielded two isomeric productsanti-Ru₂(CO)₆[μ-η ³-η ¹-MeO₂C(H)CCC(H)CO₂Me],1 in 70% yield andsyn-Ru₂(CO)₆[μ-η ³-η ¹-MeO₂C(H)CCC(H)CO₂Me],2 in 5% yield. Both compounds were characterized by single crystal X-ray diffraction analysis. Both products are diruthenium complexes with bridging di(carboxylate)allene ligands in which the oxygen atom of the carbonyl group of one of the carboxylate groupings is coordinated to one of the metal atoms. Compound1 isomerizes partially to2 at 68°C. Crystal Data for1: space group=P2₁/n,a=11.131(1) Å,b=10.228(2) Å,c=15.978(2) Å,β=102.01(1)°,Z=4, 1653 reflections,R=0.025; for2: space group=P $\bar 1$ ,a=9.340(1) Å,b=14.925(4) Å,c=6.778(2) Å,α=99-02(2)°,β=104 62(2)°,γ=94.58(2)°,Z=2, 1857 reflections,R=0.027.     

Monosubstituted Trinuclear and Tetranuclear VIB Metal Carbonyl Complexes: Syntheses of [{M(CO)5}3(Pf-Pf-Pf)] [Pf-Pf-Pf = PhP(CH2CH2PPh2)2] and [{M(CO)5}4(P-Pf3)] [P-Pf3 = P(CH2CH2PPh2)3] (M = Cr,Mo) and Crystal Structures of the Latter Three

The triligate trimetallic complexes, [{M(CO)₅}₃(Pf-Pf-Pf)] and tetraligate tetrametallic complexes, [{M(CO)₅}₄(P-Pf₃)] (M = Cr and Mo), were prepared from [M(CO) ₆] and the corresponding ligands in MeCN/CH₂Cl₂ promoted by Me₃NO at 0 °C. Crystals of trimer lb are monoclinic, space group P 2₁/n, with a = 13.407(3), b = 15.002(5), c = 26.52(1) Å, β = 90.65(2)°, Z = 4, and R = 0.060 for 2760 observed reflections. Crystals of tetramer 2a are monoclinic, space group P 2₁/c, with a – 14.183(8), b = 29.880(4), c = 16.103(2) Å, β = 94.98(3)°, Z = 4, and R = 0.039 for 5014 observed reflections. Crystals of 2b are monoclinic, space group C 2/c, with a = 42.120(8), b = 13.679(1), c = 23.486(2) Å, β = 92.14(1)°, Z = 8, and R = 0.032 for 6897 observed reflections. Each phosphorus atom of the ligands is coordinated to the M(CO)₅ moiety in each title compounds. The geometry of the four metals is a distorted tetrahedron for the tetramers.     

Preparation,crystal structure and mechanism of thermal decomposition of complex [Dy(<Emphasis Type="Italic">p</Emphasis>-MOBA)<Subscript>3</Subscript>Phen]<Subscript>2</Subscript>

1,10-Phenanthrolinetris(4-methoxybenzoate)dysprosium, Dy(p-MOBA)₃Phen (where p-MOBA = p-methoxybenzoate and Phen = 1,10-phenanthroline), (I) has been synthesized. The complex was characterized by various techniques including elemental analysis, UV, IR, XRD, molar conductance, and TG-DTG. The crystals consist of binuclear molecules and monoclinic, space group P2 ₁/n: a = 14.143(6) Å, b = 17.550(7) Å, c = 14.493(6) Å, β = 117.357(4)°, Z = 2, ρ _c = 1.655 g cm^?3, F(000) = 1588; R ₁ = 0.0176, wR ₂ = 0.0455. In the complex, each Dy³⁺ ion is nine-coordinate to one 1,10-phenanthroline molecule, one bidentate chelating carboxylate group, and four bridging carboxylate groups in which the carboxylate groups are bonded to the Dy³⁺ ions in three modes: bridging bidentate, bridging tridentate, and chelating bidentate. The thermal decomposition mechanism of I has been determined on the basis of thermal analysis. In addition, the lifetime equation at a weight-loss of 10% was deduced as lnτ = ?28.8361 + 19478.37/T by isothermal thermogravimetric analysis.