Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XLIV. Tetrakis(alkoxycarbonylmethyl)titan-Verbindungen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLIII. Tetrakis(alkoxycarbonylmethyl)titanium Compounds Organotitanium(IV) compounds of the type (ROCOCH₂)₄Ti (R ? C₂H₅, i-C₃H₇, t-C₄H₉, C₆H₅, C₆H₅CH₂) were obtained by reactions of ROCOCH₂Li derivatives with TiCl₄ at low temperature. The compounds which decompose only above 90°C were characterized by the hydrolysis products, anaerobic reactions with iodine, and the i.r. spectra. The bond conditions are discussed.     

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.     

Das verhalten von tetraalkylstannanen gegenüber flüssigem schwefeldioxid bei anwesenheit von 2,2′-bipyridyl

The SO₂ insertion into (CH₃)₄Sn and (C₂H₅)₄Sn is essentially facilitated in the presence of 2,2′-bipyridine according to eqns. (1) and (3). The corresponding bis(sulfinates) R₂Sn(O₂SR)₂ (R = CH₃, C₂H₅) are obtained in both cases at ?30°; their formation proceeds via the monosulfinates R₃SnO₂SR (R = CH₃, C₂H₅) according to eqns. (2) and (4). By this way (CH₃)₂Sn(O₂SCH₃)₂ could be prepared for the first time as a result of the SO₂ insertion into (CH₃)₄Sn.     

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).     

Synthetic and Structural Studies on the Cyclic Bis(amino)stannylenes Sn[(NR)2C10H6‐1, 8] and their Reactions with SnCl2 or Si[(NCH2But)2C6H4‐1, 2] (R = SiMe3 or CH2But)

Treatment of {HNR}₂C₁₀H₆‐1, 8 [R = SiMe₃ ( 1 ), CH₂Bu^t ( 2 )] with Sn[N(SiMe₃)₂]₂ afforded the cyclic stannylene Sn[{NR}₂C₁₀H₆‐1, 8] [R = SiMe₃ ( 3 ), CH₂Bu^t ( 4 )]. From 3 and SnCl₂ in THF and crystallisation from toluene, the product was the crystalline tetracyclic compound ( 5 ) as the (toluene)_0.5‐solvate. Reaction of 4 with the silylene Si[(NCH₂Bu^t)₂C₆H₄‐1, 2] ( 6 ) [abbreviated as Si(NN)] in benzene and crystallisation in presence of Et₂O furnished the crystalline tricyclic complex Sn[{Si(NCH₂Bu^t)₂C₆H₄‐1′, 2′}₂‐{(NCH₂Bu^t)₂C₁₀H₆‐1, 8}] ( 7 ) as the Et₂O‐solvate. Complex 5 slowly dissociated into its factors 3 and SnCl₂ in toluene, but rapidly in THF. Solutions of 7 in C₆D₆, C₇D₈ or THF‐d₈, studied by multinuclear, variable temperature NMR spectroscopy, revealed the presence of an equilibrium between 8 (an isomer of 7 , in which the skeletal atoms of the eight‐membered ring were , rather than the of 7 ) and 4 + 2 Si(NN), with 8 dominant in PhMe but not in THF; additionally 8 was shown to be fluxional and solutions of 8 in C₆D₆ or C₇D₈ decomposed to give the silane Si(NN)[(NCH₂Bu^t)₂C₁₀H₆‐1, 8], 6 and Sn metal. The X‐ray structures of 3 , 5 and 7 are presented.     

DECARBONYLATION OF ACYLCHLOROBIS-(TRIPHENYLPHOSPHINE) PLATINUM(II) COMPLEXES PROMOTED BY TIN(II) CHLORIDE

Abstract

While it might be expected that the availability of vacant coordination sites in the four coordinate acyl complexes trans[Pt(PPh₃)₂ (RCO)Cl] provides low energy pathways for alkyl and aryl migration and subsequent decarbonylation, the decarbonylation has been previously achieved only at elevated temperatures. The addition of SnCl₂ greatly facilitates decarbonylation of [Pt(PPh₃)₂ (RCO)Cl] where R is CH₃, C₂ H₅, Y[sbnd]C₆ H₄. Compounds of the type [Pt(PPh₃)₂ (RCO)SnCl₃] and [Pt(PPh₃)₂ R(SnCl₃)] have been isolated. The removal of SnCl₂ from these compounds has been achieved with ethanol. A kinetic study of the decarbonylation of [Pt(PPh₃)₂ (RCO)SnCl₃] (where R is CH₃, C₂ H₅, Y[sbnd]C₆ H₄ for Y=H, CH₃, CH₃ O, NO₂, Cl) is reported. The role of 3 and 5 coordinate intermediates in alkyl-aryl migrations in Pt(II) systems is discussed.     

The reactivity of tributyltin oxygen compounds with CCl4: Implications for its use as an extraction/reaction solvent

A variety of tributyltin oxygen compounds,(nC₄H₉)₃SnOX where X = Sn(nC₄H₉)₃, C₂H₅, nC₄H₉, C₈H₁₇, CH₂C₆H₅, COCH₃, have been studied in refluxing CCI₄. A reaction was observed to occur where X = C₂H₅, C₄H₉, C₈H₁₇, CH₂C₆H₅, leading to the formation of (nC₄H₉)₃SnCl, CHCl₃ and an aldehyde. Possible reaction pathways are suggested. These reactions have implications for the use of CCl₄ as an extraction/reaction solvent.     

Some novel triorganotin(IV) derivatives of β, δ-triketones

Thirty triorganotin(IV) derivatives of the type R₃Sn(R′COCHCOCH₂COR″) and [R₃Sn]₂ (R′COCHCOCHCOR″) (where R = CH₃, C₂H₅, nC₃H₇, nC₄H₉ and C₆H₅ and R′ = R″ = CH₃, C₆H₅ or R′ = C₆H₅, R″ = CH₃) have been synthesised by the interaction of R₃SnCl with mono- or disodium salt of 2, 4, 6-heptanetrione, 1-phenyl-1, 3, 5-hexanetrione and 1, 5-diphenyl-1, 3, 5-pentanetrione in 1:1 and 2:1 molar ratios, respectively. The complexes have been examined by their molecular weight, IR, PMR and elemental analyses and their tentative structures assigned. Both “Z” and “E” forms have been identified in the 1:1 complexes in equilibrium with the enol form containing five coordinate tin. The 2:1 derivatives contain one five- and other four coordinated tin(IV) except the phenyl analogue where both the tins are five coordinated.     

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.     

Darstellung und Eigenschaften von Diorganyl-bis(seleninato-O,O′)-Komplexen des Bleis und Zinns

Preparation and Properties of Diorganyl-bis(seleninato-O,O′) Complexes of Lead and Tin The colourless, thermically stable diorganyl-bis(seleninato-O , O ′) complexes of lead and tin R₂E(O₂SeR′)₂[E = Pb (1) , Sn (2) ] are obtained by reaction of diorganyllead- and -tindichlorides R₂ECl₂ (R = C₆H₅, CH₃, C₂H₅, n-C₄H₉) with different sodiumseleninates R′SeO₂Na (R′ = C₆H₅, CH₃, C₂H₅) at 20°C. On the basis of their i.r., Raman, and Mößbauer spectra and their slightly solubility in all organic solvents a polymeric structure is supposed in which each two R′SeO₂ - ligands are linking two lead and tin atoms respectively (c.n. = 6) intermolecular (seleninato-O , O ′). The organic residues are in trans-position.     

Komplexchemie polyfunktioneller Liganden. XXXI. Komplexe des Tetrakis(diphenylphosphorylmethyl)-methan mit FeCl3, SnCl4 und SbCl5

Complex Chemistry of Polyfunctional Ligands. XXXI. Complexes of Tetrakis(diphenylphosphorylmethyl) methane with FeCl₃, SnCl₄, and SbCl₅ C[CH₂P(O)(C₆H₅)₂]₄ forms with FeCl₃ the compounds C[CH₂P(O)(C₆H₅)₂]₄ · 2FeCl₃ and C[CH₂P(O)(C₆H₅)₂]₄ · 4 FeCl₃. From their IR spectra ionic, spirocyclic structures have been derived. C[CH₂P(O)(C₆H₅)₂]₄ yields with SnCl₄ and SbCl₅ also spirocyclic compounds of the composition C[CH₂P(O)(C₆H₅)₂]₄ · 2 SnCl₄ and C[CH₂P(O)(C₆H₅)₂]₄ · 4 SbCl₅, but the SnCl₄ derivative has a nonionic structure.     

Neue Synthesewege für Organohalogenstibane

New Methods for Synthesis of Organohalogenostibanes Organohalogenostibanes RSbX₂ (R = CH₃, C₆H₅; X = Cl, Br) and R₂SbX (R = C₆H₅; X = Cl) are received in good yields by alkylation or arylation of the corresponding antimony halides with Pb(CH₃)₄, Sn(CH₃)₄, Sb(CH₃)₃, or Sb(C₆H₅)₃. These methods are better than those, described in the literature for preparation of the compounds.     

New chelated complexes of bis-β-carboalkoxyethyltin(IV) dichloride with S-benzyldithiocarbazate Schiff bases

The Schiff bases [H₂SBSaD], [H₂SBVD] and [H₂SBND], derived by the condensation of S-benzyldithiocarbazate and salicylaldehyde, 2-hydroxy-3-methoxybenzaldehyde and 2-hydroxy-1-naphthaldehyde respectively, react with diestertin dichlorides, R₂SnCl₂ [R=? CH₂CH₂CO₂CH₃, ? CH₂CH₂CO₂C₂H₅ or ? CH₂CH₂CO₂C₄H₉] in 1:1 molar proportion to yield chlorine-substituted complexes of the type R₂Sn(Schiff base), the base being tridentate. The complexes are characterized on the basis of their elemental analyses, IR and ¹H NMR spectral studies. The ¹³C and ¹¹⁹Sn NMR and the tin-carbon coupling constant data reveal the structures of the complexes to be octahedral with trans ester grouping, and bidentate ester linkages. The pentacoordinated complex (CH₃)₂Sn(SBSaD) was prepared by the reaction of dimethyltin oxide with H₂SBSaD in equimolar proportions.     

Systematische untersuchungen über das verhalten von organozinnverbindungen gegenüber flüssigem schwefeldioxid III. SO2-disproportionierung bei einschiebungsreaktionen an tetraalkylstannanen

When liquid SO₂ is allowed to react with the tetraalkyltin compounds (CH₃)₄Sn and (C₂H₅)₄Sn at 60°, disproportionation of sulfur takes place resulting in the formation of the corresponding bis(trialyltin) sulfates, [R₃Sn]₂SO₄, and alkanethiosulfonic acid S-alkyl esters, RSO₂SR (R = CH₃, C₂H₅). The course of the reaction is discussed.     

Synthesis reactivity and electrochemical properties of substituted cyclopentadienyl cobalt (III) complexes

Cyclopentadienyl cobalt complexes (η⁵‐C₅H₄R) CoLI₂ [L = CO,R=‐COOCH₂CH=CH₂ (3); L=PPh₃, R=‐COOCH₂‐CH=CH₂ (6); L=P(p‐C₆H₄O₃)₃, R = ‐COOC(CH₃) = CH₂ (7), ‐COOCH₂C₆H₅ (8), ‐COOCH₂CH = CH₂ (9)] were prepared and characterized by elemental analyses, ¹H NMR, ER and UV‐vis spectra. The reaction of complexes (η⁵‐C₅H₄R)CoLI₂ [L= CO, R= ‐COOC(CH₃) = CH₂ (1), ‐COOCH₂C₆H₅(2); L=PPh₃, R=‐COOC (CH₃) = CH₂ (4), ‐COOCH₂C₆H₅ (5)] with Na‐Hg resulted in the formation of their corresponding substituted cobaltocene (η⁵‐C₅H₄R)₂ Co[R=‐COOC(CH₃) = CH₂ (10), ‐COOCH₂C₆H₅ (11)]. The electrochemical properties of these complexes 1–11 were studied by cyclic voltammetry. It was found that as the ligand (L) of the cobalt (III) complexes changing from CO to PPh₃ and P(p‐tolyl)₃, their oxidation potentials increased gradually. The cyclic voltammetry of α,α′‐substituted cobaltocene showed reversible oxidation of one electron process.     

Substituted Diorganotin(IV) O,O’-Alkylene Dithiophosphates: Synthesis and Spectral Aspects

Six new substituted diphenyltin(IV) O,O′-alkylene dithiophosphates, (C₆H₅)₂Sn(X)S(S) POGO [G = —CH₂C(CH₃)₂CH₂—, X = Cl (1), SCN (3), ClO₄ (5); G = —CH₂C (C₄H₉)(C₂H₅)CH₂—, X = Cl (2), SCN (4), ClO₄ (6)], were synthesized by the reaction of the corresponding ammonium salts of the O,O’-alkylene dithiophosphates with an appropriate organotin(IV) chloride. The compounds were characterized on the basis of elemental and spectral analyses (ESI mass spectrometry, IR, ¹H, ¹³C, ³¹P, and ¹¹⁹Sn NMR). The presence of a four-coordinated Sn atom and monodentate O,O’-alkylene dithiophosphate moiety in compounds 1–4 as well as bidentate O,O’-alkylene dithiophosphate unit in compounds 5,6 is established.     

New Dinuclear Ru2(CO)4 Sawhorse‐Type Complexes Containing Bridging Carboxylato Ligands

The thermal reaction of Ru₃(CO)₁₂ with ethacrynic acid, 4‐[bis(2‐chlorethyl)amino]benzenebutanoic acid (chlorambucil), or 4‐phenylbutyric acid in refluxing solvents, followed by addition of two‐electron donor ligands (L), gives the diruthenium complexes Ru₂(CO)₄(O₂CR)₂L₂ ( 1 : R = CH₂O‐C₆H₂Cl₂‐COC(CH₂)C₂H₅, L = C₅H₅N; 2 : R = CH₂O‐C₆H₂Cl₂‐COC(CH₂)C₂H₅, L = PPh₃; 3 : R = C₃H₆‐C₆H₄‐N(C₂H₄‐Cl)₂, L = C₅H₅N; 4 : R = C₃H₆‐C₆H₄‐N(C₂H₄‐Cl)₂, L = PPh₃; 5 : R = C₃H₆‐C₆H₅, L = C₅H₅N; 6 : R = C₃H₆‐C₆H₅, L = PPh₃). The single‐crystal structure analyses of 2 , 3 , 5 and 6 reveal a dinuclear Ru₂(CO)₄ sawhorse structure, the diruthenium backbone being bridged by the carboxylato ligands, while the two L ligands occupy the axial positions of the diruthenium unit.     

Trimethylstannyl- und Dimethylstannyl-substituierte Pyrrole – Synthesen,Spektren und Strukturen

Trimethylstannyl- and Dimethylstannyl-substituted Pyrroles – Synthesis, Spectra, and Structures Monomeric trimethylstannyl pyrroles, Me₃Sn? R (Me = CH₃ and R = ? NC₄H₄, ? NC₄H₂Me₂-2,5, ? NC₄Me₄-2,3,4,5, ? C₄H₃NMe-1), are synthesized by metathesis reactions from Me₃SnCl with 1(N)- and 2(C)-lithium pyrroles, respectively. An almost similar procedure gives monomeric dimethylstannylbis(pyrroles), Me₂SnR₂ ( 1 a – 3 a ), from Me₂SnCl₂ and 1-Li-pyrrolides (1 : 2 molar ratio) in good yields. Lithiated 1,2,5-trimethylpyrrole and Me₃SnCl forms the compound Me₃Sn? CH₂? C₄H₂Me(-5)NMe ( 8 ), the reaction of Me₂SnCl₂ with 2-lithium-1-methylpyrrole gives oligomeric [Me₂Sn? C₄H₂NMe? ]_x, ( 6 a ). The mass-, NMR, and vibrational spectra have been measured and discussed. The results of the X-ray structure determinations of Me₃Sn? NC₄H₄ ( 1 ) and Me₂Sn(? NC₄Me₄)₂ ( 3 a ) are compared with the structures of the known dimethylmetal pyrroles of Al, Ga, and In.     

Studies on organophosphorus compounds XLVIII Synthesis of Dithioesters from P,S-Containing Reagents and Carboxylic Acids and Their Derivatives

2,4-Bismethylthio-1,3,2,4-dithiadiphosphetane 2,4- disulfide, IIa, is prepared from 0,0-dimethyldithiophosphoric acid, Ia, and P₄S₁₀ at 160°C. 2,4-Bis(4-phenoxyphenyl)-1,3,2,4- dithiadiphsophetane 2,4-disulfide, IIc, and 2,4-bis(4-phenylthiolophenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide, IId, are prepared at l60°C from P₄ S₁₀ and diphenylether and diphenylsulfides, respectively. Carboxylic acids RCOOH(R = CH₃ C₂H₅, n-C₃H₇, n-C₄H₉, C₆H₅CH₂, C₆H₈) react with compound Ia at 130°C to give the corresponding methyl dithioesters. Carboxylic acids RCOOH (R = C₆H₈-CH₂, C₆H₈) react with compound Ib at 200°C for 15 min to give the corresponding ethyl dithioesters, while low boiling acids (R = CH₃, C₂H₈, n-C₃H₇) yielded mixtures of the corresponding ethyl dithioester and ethyl carboxylate. Carboxylic acid chlorides RCOCl (R = ClCH₂, C₂H₅, t-C₄H₅ C₆H₅CH₂, C₆H₅, P-NO₂C₆H₄) react with compound IIa at 80°C to give the corresponding methyl dithioesters in good yields. S-Substituted thioesters react with IIC at 85°C to give the corresponding dithioesters in good yields. Dihydro2(3H)-furanone, VI, and 5-methyl-2(3H)-furanone, VII, react with IIa at 80°C; to dihydro-2(3H)-thiophenethione, VIII and 2,2'-dithiobis(5-methyl thiophene),IX, respectively. Also XI reacts with IIa,IIc, and IId to give VIII in nearly quantitative yields.     

Synthesis and structural characterizations of diorganotin(IV) complexes with 2-pyrazinecarboxylic acid

Two types of diorganotin(IV) complexes {[R₂Sn(O₂CC₄H₃N₂)]₂O}₂ (R = n-octyl 1, 2-ClC₆H₄CH₂3, 2-FC₆H₄CH₂5, 4-FC₆H₄CH₂7) and R₂Sn(O₂CC₄H₃N₂)₂ (R = n-octyl 2, 2-ClC₆H₄CH₂4, 2-FC₆H₄CH₂6, 4-FC₆H₄CH₂8) were prepared by reactions of diorganotin oxide with 2-pyrazinecarboxylic acid. The complexes 1-8 are characterized by elemental analysis, IR and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopies. The complexes {[(n-C₈H₁₇)₂Sn(O₂CC₄H₃N₂)]₂O}₂ (1) and (n-C₈H₁₇)₂Sn(O₂CC₄H₃N₂)₂ (2) are also determined by X-ray single crystal diffraction, which reveal that the endo-cyclic tin atom of complex 1, is seven-coordinate, and the exo-cyclic tin atom is hexa-coordinated geometry, while the complex 2 is seven-coordinated geometry. The nitrogen atom of the aromatic ring participates in the interactions with the Sn atom.