Reactions of dichlorobis(cyclopentadienyl)titanium (IV) with multidentate Schiff bases

Summary Dichlorobis(cyclopentadienyl)titanium(IV), Cp₂TiCI₂, reacts with bidentate Schiff bases such as salicylideneaniline, salicylidene-o-toluidine, salicylidene-m-toluidine, salicylidene-p-toluidine and 2-hydroxy-l-naphthylReprints of this paper are not available.To whom all correspondence should be addressed.     

Lanthanon (III) Derivatives of Monofunctional Bidentate Schiff Bases

The 1:1, 1:2 and 1:3 interactions of lanthanon (III) isopropoxide with monofunctional bidentate Schiff bases as salicylidene-o-toluidine (SOTH) and salicylidene-p-p-toluidine (SPTH) have been investigated. The resulting products Ln(OPr¹)₂(SB), Ln(OPr¹)(SB)₂ and Ln(SB)₃ (where Ln=Pr, Nd and Sm and SB^1? is the anion of the corresponding Schiff base) have been isolated in almost quantitative yields. The infrared spectra of these compounds have been recorded and plausible structures suggested.     

Mono- and bisphenoxy derivatives of bis(indenyl) titanium(IV)

A series of (C₉H₇)₂Ti(OAr)Cl and (C₉H₇)₂Ti(OAr)₂ complexes whereAr=C₆H₅,p-ClC₆H₄, α-C₁₀H₇ or β-C₁₀H₇, have been synthesised by the reaction of bis(indenyl) titanium(IV) dichloride with an appropriate phenol in a 1:1 and 1:2 molar ratio in refluxing benzene in the presence of triethylamine. The new derivatives have been characterized on the basis of their elemental analyses, conductance measurements and spectral (IR,¹H-NMR and electronic) studies.     

Mono- and bisphenoxy derivatives of bis(indenyl)zirconium(IV)

A series of (C₉H₇)₂Zr(OAr)Cl and (C₉H₇)₂Zr(OAr)₂ complexes, where Ar = C₆H₅, p-ClC₆H₄, α-C₁₀H₇, or β-C₁₀H₇, have been synthesised by the reaction of bis(indenyl)zirconium(IV)-dichloride with an appropriate phenol in a 1:1 and 1:2 molar ratio in refluxing benzene in the presence of triethylamine. These complexes have been characterised by elemental analyses, conductance measurements and spectral (IR, ¹H NMR and electronic) studies.     

Reactions of silylated Schiff bases with organotitanium(IV) and organotin(IV) chlorides

The interactions of silylated dibasic quadridentate Schiff bases derived fromo-hydroxyacetophenone and ethylenediamine and orthophenylenediamine with (π-C₅H₅)TiCl₃, (π-C₅H₅)(MeO)TiCl₂, (MeO)₂TiCl₂, Me₂SnCl₂ and MeSnCl₃ yield a new series of organotitanium(IV) and tin(IV) compounds. The reactivity of (π- C₅H₅)Ti(L₁)Cl and MeSn(L₁)Cl, towards MeSH, Me₂NSiMe₃, SiMe₃N₃ and Me₃SiC = CPh are also described. The structures for the compounds isolated are proposed on the basis of elemental analyses, molecular weights, IR and¹H nmr spectroscopic studies.     

Tin(IV) complexes of schiff bases derived from pentane-2,4-dione or 2-hydroxy-1-naphthaldehyde

The 1∶2 molar reactions of tin(IV) chloride with the Schiff bases, CH₃C(OH):CHC(CH₃):NR and 2 HOC₁₀H₆CH:NR′ (where R=C₂H₅,n-C₃H₇ orn-C₄H₉ and R′=C₆H₅, C₂H₅,n-C₄H₉ ort-C₄H₉) have resulted in the synthesis of SnCl₄·(SBH)₂ type derivatives (whereSBH represents the Schiff base molecule). These have been characterized by elemental analysis, conductivity measurements and IR spectral studies.     

Studies on monocyclopentadienyl titanium(IV) dithiocarbamato complexes

Titanium(IV) dithiocarbamato complexes of the typesCpTi(S₂CNHR)Cl₂ andCpTi(S₂CNHR)₂Cl, whereR=C₈H₅N₂S, C₉H₅N₂SCl₂ and C₉H₇N₂S, have been prepared by the reaction of monocyclopentadienyl titanium(IV) trichloride with the potassium salt of the appropriate dithiocarbamic acid in anhydrous dichloromethane. Conductance and infrared studies indicate that these complexes are non-electrolytes in which all dithiocarbamate ligands are bidentate. Therefore, 5 and 6 coordinate structures can be assigned toCpTi(S₂CNHR)Cl₂ andCpTi(S₂CNHR)₂Cl complexes, respectively.¹H-NMR spectra indicate that there is rapid rotation of the cyclopentadienyl ring about the metal ring axis.

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Untersuchungen von Monocyclopentadienyl-titan(IV)-dithiocarbamat-Komplexen

Zusammenfassung Es wurden Titan(IV)-dithiocarbamat-Komplexe vom TypCpTi(S₂CNHR)Cl₂ undCpTi(S₂CNHR)₂Cl mitR=C₈H₅N₂S, C₉H₅N₂SCl₂ und C₉H₇N₂S mittels der Reaktion von Monocyclopentadienyltitan(IV)trichlorid mit dem Kaliumsalz der entsprechenden Dithiocarbaminsäure in wasserfreiem Dichlormethan dargestellt. Leitfähigkeitsmessungen und IR-Untersuchungen zeigen, daß diese Komplexe Nichtelektrolyte sind, bei denen alle Dithiocarbamat-Liganden zweizähnig sind. Demnach können 5-, bzw. 6-koordinierte Strukturen für die Komplexe des TypsCpTi(S₂CNHR)Cl₂, bzw.CpTi(S₂CNHR)₂Cl angenommen werden. Die¹H-NMR Spektren zeigen eine rasche Rotation des Cyclopentadienylrings um die Metall-Ring Achse an.

     

Schiff base derivatives of titanium(IV) and zirconium(IV)

The reactions of a few bifunctional and tridentate Schiff bases with titanium-(IV) and zirconium(IV) isopropoxides in equimolar and bimolar ratios are described. The resulting compounds have been obtained in almost quantitative yields and are of the general formulae M(SB)_x(OPrⁱ)_4?2X (where M = Ti or Zr; SB- = anion of the Schiff base SBH₂ and x = 1 or 2). Their molecular weights have been determined ebullioscopically and IR spectra recorded.     

Reversible oxidative addition of a diaryl diselenide to a diorganopalladium(II) complex, carbon-selenium bond formation at palladium(IV), and structural studies of palladium(II) and platinum(IV) selenolates

Methyl(4-methoxyphenyl)(2,2^′-bipyridine)palladium(II) (1) reacts with bis(4-chlorophenyl) diselenide in dichloromethane to form an equilibrium with the Pd(IV) complex Pd(SeC₆H₄Cl)₂Me(C₆H₄OMe)(bpy) (2) for which the forward reaction exhibits ΔH=−130±12 kJ mol⁻¹ and ΔS=−472±49 J K⁻¹ mol⁻¹, and with K=754±145 at −25 °C. The Pd(IV) complex is isolable at −40 °C, and when the equilibrium mixture is kept at −25 °C, a temperature at which the Pd(II) complex is stable, selective reductive elimination of Me-SeC₆H₄Cl occurs very slowly from the Pd(IV) complex to form Pd(SeC₆H₄Cl)(C₆H₄OMe)(bpy) (3). In contrast, (ClC₆H₄Se)₂ reacts with PdMe₂(dmpe) (4) [dmpe=1,2-bis(dimethylphosphino)ethane] to form Pd(SeC₆H₄Cl)Me(dmpe) (5) and Me-SeC₆H₄Cl. A second equivalent of (ClC₆H₄Se)₂ reacts with 5 to cleave the second Pd-Me bond to give Pd(SeC₆H₄Cl)₂(dmpe) (6) and Me-SeC₆H₄Cl. Similarly, PdMeTol(dmpe) (7) (Tol=4-tolyl) forms predominantly Pd(SeC₆H₄Cl)Tol(dmpe) (8) together with some Pd(SeC₆H₄Cl)Me(dmpe) (5), and 8 reacts with (ClC₆H₄Se)₂ to form Pd(SeC₆H₄Cl)₂(dmpe) (6) and Tol-SeC₆H₄Cl. Bis(4-chlorophenyl) diselenide reacts with PtTol₂(bpy) (9) (Tol=4-tolyl) to form Pt(SeC₆H₄Cl)₂Tol₂(bpy) (10) which, together with 2, has a trans-configuration for the selenolate ligands. X-ray structural studies of octahedral 10 as the solvate 10 · 3CHCl₃ and square planar 5 are reported.     

Thermal studies of some biologically active oxovanadium(IV) complexes containing 8-hydroxyquinolinate and hydroxamate ligands

The thermal decomposition behaviours of oxovanadium(IV)hydroxamate complexes of composition [VO(Q)_2?n(HL^1,2)_n]: [VO(C₉H₆ON)(C₆H₄(OH)(CO)NHO)] (I), [VO(C₆H₄(OH)(CO)NHO)₂] (II), [VO(C₉H₆ON)(C₆H₄(OH)(5-Cl)(CO)NHO)] (III), and [VO(C₆H₄(OH)(5-Cl)(CO)NHO)₂] (IV) (where Q?=?C₉H₆NO^? 8-hydroxyquinolinate ion; HL¹?=?[C₆H₄(OH)CONHO]^? salicylhydroxamate ion; HL²?=?[C₆H₃(OH)(5-Cl)CONHO]^? 5-chlorosalicylhydroxamate ion; n?=?1 and 2), which are synthesised by the reactions of [VO(Q)₂] with predetermined molar ratios of potassium salicylhydroxamate and potassium 5-chlorosalicylhydroxamate in THF?+?MeOH solvent medium, have been studied by TG and DTA techniques. Thermograms indicate that complexes (I) and (III) undergo single-step decomposition, while complexes (II) and (IV) decompose in two steps to yield VO(HL^1,2) as the likely intermediate and VO₂ as the ultimate product of decomposition. The formation of VO₂ has been authenticated by IR and XRD studies. From the initial decomposition temperatures, the order of thermal stabilities for the complexes has been inferred as III?>?I > II?>?IV.     

Diorganotin(IV) complexes of N-protected dipeptides

Eight new diorganotin(IV) complexes of general formula R₂Sn(DP)₂ and [R₂Sn(DP)]₂O (DP = anion of N-benzoyl-dl-alanylglycine; R = CH₃, C₂H₅, n-C₄H₉, n-C₈H₁₇) have been prepared and characterised by IR, and ^119mSn Mössbauer spectroscopy. However, only two complexes, (DP)₂Sn(n-C₄H₉)₂ and (DP)₂Sn(n-C₈H₁₇)₂ were sufficiently soluble for NMR (¹H and ¹³C) studies. The 2 : 1 complexes are monomeric with distorted trans-octahedral structures. The 1 : 1 complexes are dinuclear with Sn-O-Sn bridges and trigonal bipyramidal geometry about tin. In both cases the dipeptide acts as an O,O-bidentate ligand.     

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).     

Studies on Carboxylato Complexes of Tricyclopentadienyl Cerium (IV) Chloride and Bisindenyl Cerium (IV) Dichloride

Tricyclopentadienyl Cerium (IV) chloride and bisindenyl cerium (IV) dichloride have been treated with sodium salts of the appropriate carboxylic acids in benzene or tetrahydrofuran medium to give (C₅H₃)₃ Ce(R) and (C₉H₇)₂Ce(R)₂ wherein R is HCOO, CH₃COO, C₂H₅COO, C₃H₇COO and C₆H₅COO. The infrared spectra, thermal stabilities and other characteristics of the above compounds have been studied and reported.     

Indenylvanadium(V)‐Verbindungen. Darstellung,Struktur und NMR‐spektroskopische Untersuchungen

Indenylvanadium(V) Compounds Synthesis, Structure, and NMR Spectroscopic Studies Syntheses of the indenylvanadium(V)compounds are described: ^tC₄H₉N = V(η⁵‐C₉H₇)Cl₂ ( 1 ), ^tC₄H₉N = V(η⁵‐C₉H₇)Br₂ ( 2 ), ^tC₄H₉N = V(η⁵‐C₉H₇)(O^tC₄H₉)Cl ( 3 ), ^tC₄H₉N = V(η¹‐C₉H₇)(O^tC₄H₉)₂ ( 4 ), ^tC₄H₉N = V(η¹‐C₉H₇)₂(O^tC₄H₉) ( 5 ), ^tC₄H₉N = V(η¹‐C₉H₇)(η⁵‐C₅H₅) · (O^tC₄H₉) ( 6 ), ^tC₄H₉N = V(η¹‐C₉H₇)(η⁵‐C₅H₅)(NH^tC₄H₉) ( 7 ). All compounds were totally characterized by spectroscopic methods (MS; ¹H, ¹³C, ⁵¹V NMR), 3 by single crystal X‐ray diffraction. For 6 the presence of the diastereomeres RR/SS and RS/SR was shown by NMR spectroscopy. The chlorovanadate (IV) complex [NHC₄H₉]₂⁺[(^tC₄H₉N)₇V₇ · (μ‐Cl)₁₄Cl₂]^2– has been obtained by decomposition of 1 in solution; the crystal structure indicates a wheel structure with hydrogen bonds between the tert‐butylammonium cations and the complex anion.     

Between MOFs and molecules: organolead(IV) compounds with chain structures

Organolead compounds are of interest mainly as catalysts and organolead halides have proved to be very efficient materials for solar cells. Two organolead(IV) dimethylarsinates, namely catena‐poly[[triphenyllead(IV)]‐μ‐chlorido‐[triphenyllead(IV)]‐μ‐dimethylarsinato‐κ²O:O′], [Pb₂(C₆H₅)₆(C₂H₆AsO₂)Cl]_n or [(Ph₃Pb)₂Cl(O₂AsMe₂)], ( 1 ), and poly[chlorido(μ₃‐dimethylarsinato‐κ³O:O,O′:O′)diphenyllead(IV)], [Pb(C₆H₅)₂(C₂H₆AsO₂)Cl]_n or [(Ph₂ClPb)(O₂AsMe₂)], ( 2 ), together with the triphenyllead(IV) diphenylphosphinate catena‐poly[[triphenyllead(IV)]‐μ‐diphenylphosphinato‐κ²O:O′], [Pb(C₆H₅)₃(C₁₂H₁₀O₂P)]_n or [(Ph₃Pb)(O₂PPh₂)], ( 3 ), have been synthesized and characterized by single‐crystal X‐ray diffraction, IR spectroscopy and mass spectrometry. In ( 1 ), a chain structure was found with alternating chloride and Pb—O—As—O—Pb arsinate bridges between five‐coordinate Pb^IV atoms. In ( 2 ), bidentate and chelate‐like bonded dimethylarsinate ligands form double chains with heptacoordinated Pb^IV atoms. In ( 3 ), a pentacoordinated Pb^IV atom is connected by Pb—O—P—O—Pb phosphinate bridges to form a linear chain. Obviously, the steric demand of the phenyl ligands at Pb^IV reduces the possibility of interconnections via polydentate ligands to one dimension only. Thus, no metal–organic frameworks (MOF) are formed but instead various chain structures are observed.     

Synthesis,spectroscopic and structural characterization of diphenyltin(IV) complexes of acetone Schiff bases of S-alkyldithiocarbazates

New diphenyltin(IV) complexes of empirical formula, [Sn(C₆H₅)₂(NS)Cl] (NS = anionic forms of the acetone Schiff bases of S-methyl or S-benzyldithiocarbazate) have been prepared and characterized by IR, NMR and Mössbauer spectroscopic techniques. The crystal and molecular structures of the acetone Schiff bases of S-methyldithiocarbazate (Hacsme) and S-benzyldithiocarbazate (Hacsbz) and their tin(IV) complexes have been determined by X-ray diffraction. In the solid state, both the Schiff bases exist in their thioketo tautomeric forms with the azomethine nitrogen atom trans to the thione sulfur atom but in the tin(IV) complexes they are present in their deprotonated ene-thiolate forms being coordinated to the tin atom as bidentate chelating agents via the azomethine nitrogen and thiolate sulfur atoms. The tin atom adopts a five-coordinate, approximately trigonal bipyramidal geometry, with the thiolate sulfur atom of the Schiff base and the two phenyl groups occupying the equatorial positions. The azomethine nitrogen atom and the chlorine ligand occupy axial positions. The distortion from a regular trigonal bipyramidal or a square-pyramidal geometry is attributed to the restricted bite sizes of the five-membered chelate rings.     

Supramolecular organotin(IV) dithiocarboxylates as potential antimicrobial agents

A series of tri-, chlorodi-, and diorganotin(IV) derivatives of 4-(2-methoxyphenyl)piperazine-1-carbodithioate (L) {R?=?n-C₄H₉ (1), C₆H₁₁ (2), CH₃ (3) and C₆H₅ (4)}, (n-C₄H₉)₂SnClL (5) and R₂SnL₂ {R?=?n-C₄H₉ (6), C₂H₅ (7), CH₃ (8)} have been synthesized by refluxing organotin(IV) chlorides with the ligand-salt in the appropriate molar ratio. Elemental analysis, Raman, IR, multinuclear NMR (¹H, ¹³C and ¹¹⁹Sn), mass spectroscopic, and single-crystal X-ray crystallographic studies were undertaken to elucidate the structures of the new compounds both in solution and in the solid state. The X-ray diffraction work reveals supramolecular structures for 4 and 6, with distorted trigonal-bipyramidal and distorted octahedral geometries around Sn, respectively. The ligand and several of the new compounds are good antimicrobial agents.     

ESR Characterization of Two Oxovanadium (IV) Schiff Base Complexes Derived from Tris(2-aminoethyl)amine

The compounds, C₂₁H₂₇N₄O₃(L¹) and C₂₁H₂₇N₇(L²), is a tripodal Schiff base that was obtained from the reaction of tris(2-aminoethyl)amine (tren) and furan-2-carbaldehyde and pyrole- 2- carbaldehyde. The tripodal Schiff bases and their oxovanadium complexes have been characterized on the basis of the results of the elemental analysis, magnetic susceptibility measurements and spectroscopic studies FT-IR, ¹H-NMR, UV–Vis, ESR, magnetic moment and thermal analysis (TGA). Job's method of continuous variation shows 3:2 metal to ligand ratio.     

Bis(indenyl)zirconium(IV) complexes of monofunctional bidentate salicylidimines

A series of (C₉H₇)₂Zr(SB)Cl complexes whereSB ^– is the anion of bidentateSchiff base derived from salicylaldehyde and 4-substituted anilines, viz. salicylidene-4-ansidine, salicylidene-4-phenetidine, salicylidene-4-chloroaniline, salicylidene-4-bromoaniline, salicylidene-4-iodoaniline and salicylidene-4-nitroaniline, have been synthesized by the reaction of bis(indenyl)zirconium(IV) dichloride andSchiff base (SBH) in 1:1 molar ratio in refluxingTHF in the presence of triethylamine. The new derivatives have been characterized on the basis of their elemental analyses, conductance measurements and spectral (IR,¹H-NMR, UV-VIS) studies.

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Bis(indenyl)zirkonium(IV)-Komplexe monofunktioneller zweizähniger Salicylidimine

Zusammenfassung Es wurde eine Reihe von (C₉H₇)₂Zr(SB)Cl-Komplexen synthetisiert, wobeiSB ^– für das Anion einer zweizähnigenSchiff-Base steht. DieSchiff-Basen sind von Salicylaldehyd und 4-substituierten Anilinen hergeleitet: Salicyliden-4-anisidin,-4-phenetidin, -4-Cl-, -4-Br-, -4-I-anilin und -4-Nitroanilin. Die Synthese erfolgte über die Reaktion von Bis(indenyl)zirkonium(IV)-dichlorid mit derSchiff-Base (SBH) in einem molaren Verhältnis von 1:1 am Rückfluß in Gegenwart von Triethylamin undTHF als Lösungsmittel. Zur Charakterisierung der neuen Derivate wurden Elementaranalysen, Leitfähigkeitsmessungen und spektroskopische Daten (IR,¹H-NMR, UV-VIS) herangezogen.

     

Darstellung und Struktur der Zweikernigen tert-Butyliminovanadium(IV)-Komplexe [(μ?NtC4H9)2V2(CH2CMe3)2X2] (X = OtC4H9, CH2CMe3)

Synthesis and Molecular Structure of the Binuclear tert-Butyliminovanadium(IV) Complexes [(μ-N^tC₄H₉)₂V₂(CH₂CMe₃)₂X₂] (X = O^tC₄H₉, CH₂CMe₃) Syntheses of the neopentylvanadium(V) compounds ^tC₄H₉N?V(CH₂CMe₃)_3?n(O^tC₄H₉)_n (n = 0 ( 7 ), 1 ( 6 ), 2) are described. 6 and 7 decompose by irradiation splitting off neopentane and yielding the binuclear diamagnetic neopentylvanadium(IV) complexes [(μ-N^tC₄H₉)₂V₂(CH₂CMe₃)₂X₂] [X = O^tC₄H₉ ( 8 ), CH₂CMe₃ ( 11 )]. All compounds obtained are characterized by ¹H and ⁵¹V NMR spectroscopy. 8 has been found by X-ray diffraction analysis to be a binuclear complex with bridging tert-butylimino ligands and a vanadium—vanadium single bond. The complexes ^tC₄H₉N?V(CH₂C₆H₅)(O^tC₄H₉)₂ and [(μ-N^tC₄H₉)₂V₂(CH₂SiMe₃)₂(O^tC₄H₉)₂] ( 10 ) have been also prepared; the crystal structure of 8 and 10 are nearly identical.