Photochemical reactions of chromium hexacarbonyl with tetraalkyldiphosphine disulfides

New complexes [Cr(CO)₄(R₂P(S)P(S)R₂)] and [Cr₂(CO)₁₀(-R₂P(S)P(S)R₂)] (R = Me, Et, Pr ⁿ , Bu ⁿ ), (1a)–(1d) and (2a)–(2d) [(1a), R = Me; (1b), R = Et; (1c), R = Pr ⁿ ; (1d), R = Bu ⁿ ; (2a), R = Me; (2b), R = Et; (2c), R = Pr ⁿ ; (2d), R = Bu ⁿ ] have been prepared by the photochemical reaction of Cr(CO)₆ with R₂P(S)P(S)R₂ (R = Me, Et, Pr ⁿ and Bu ⁿ ) and characterized by elemental analyses, FT-i.r., ³¹P-[¹H]-n.m.r. spectroscopy and FAB-mass spectrometry. The spectroscopic data suggest cis-chelate bidentate coordination of the ligand in [Cr(CO)₄(R₂P(S)P(S)R₂)] and cis-bridging bidentate coordination of the ligand between two metals in [Cr₂(CO)₁₀(-R₂P(S)P(S)R₂)] (R = Me, Et, Pr ⁿ and Bu ⁿ ).     

Synthesis,Characterization, and Sol-Gel Behavior of Dichlorotitanium(IV) (O-Alkyl,O-Cycloalkyl,and O-Aryl Trithiophosphates)

Dichlorotitanium(IV) trithiophosphates of the type TiCl₂[(RO)P(S)S₂] (where R = Me, Et, Prⁿ, Prⁱ, Buⁿ, Bu^s, Buⁱ, Amⁱ, Ph and cyclohexyl) have been synthesized for the first time by the reaction of titanium tetrachloride with potassium trithiophosphates in a 1:1 molar ratio in anhydrous benzene. Sol-gel chemistry of these titanium(IV) compounds has been studied in dry benzene by treatment with hydrogen sulfide gas. These newly synthesized derivatives have been characterized by elemental analysis (C, H, S, Cl, and Ti), molecular weight measurement, and spectral [IR and multinuclear NMR (¹H, ¹³C, and ³¹P)] studies. The bonding mode of trithiophosphate ligands and tentative structure around titanium(IV) are discussed.     

O-Alkyl Trithiophosphate Derivatives of Triorganotin(IV) and S-Alkyl Trithiophosphate Derivatives of Diorganotin(IV) Chloride

Reactions of triorganotin chlorides with potassium salt of O-alkyl trithiophosphate [ROP(S)(SK)₂; R = Me, Prⁱ, Ph] in 2:1 molar ratio in anhydrous benzene yield triorganotin O-alkyl trithiophosphate of the type ROP(S) [SSnR′₃]₂ R = Me, Prⁱ; Ph, R′ = Prⁿ, Buⁿ, Ph] which are found to be monomeric in nature. These complexes are soluble in common organic solvents. Similar reactions of diorganotin chloride with dipotassium salt of S-alkyl trithiophosphate yield diorganotin-S-alkyl trithiophosphate of the type [(RS)P(O)S₂]₂SnR′₂; R = Me, Prⁱ; R′ = Me, Et, Ph, which also are found to be monomeric in nature and are soluble in common organic solvents. The newly synthesized derivatives have been characterized by physicochemical and spectroscopic techniques, IR, NMR (¹H, ³¹P, and ¹¹⁹Sn).     

SYNTHESIS AND CHARACTERIzATION OF TRIPHENYLANTIMONY (V) (O-ALKYL,O-CYCLOALKYL AND O-ARYLTRITHIOPHOSPHATES)

Triphenylantimony (V) (O-alkyl,O-cycloalkyl and O-aryltrithiophosphates) of the type Ph ₃ Sb[S ₂ (S)P(OR)] (R = Me, Et, Pr ⁿ , Pr ⁱ , Bu ⁿ , Bu ^s , Bu ⁱ , Am ⁱ , Ph and C.h. = cyclohexyl) have been synthesized for the first time by the reaction of triphenylantimony (V) dibromide with potassium trithiophosphates in 1:1 molar ratio in methanol. These new compounds have been characterized by elemental analysis, molecular weight determinations, and spectroscopic (IR,¹³C and ³¹P NMR) studies. On the basis of these data trigonal bipyramidal geometry has been proposed for these compounds.     

Alkylxanthates of phenylarsenic(III)

Bis-xanthates of phenylarsenic(III), having the general formula, PhAs(S₂COR)₂ (where R = Me, Et, Prⁿ, Prⁱ, allyl and Buⁿ), have been synthesized and characterized by elemental analysis, molecular weight, IR, NMR (¹H and ¹³C) and mass spectral data which have been discussed in relation to plausible structures for these arsenic derivatives.     

Synthesis and spectral studies of diorganotin(IV) dialkyldithiophosphates

Two series of diorganotin(IV) dialkyldithiophosphates, [RR′Sn{SSP(OR″)₂}₂](R = Me or Et; R′= Ph; R″ = Et, Prⁿ, Prⁱ or Buⁿ) and [RR′Sn(Cl){SSP(OR″)₂}] (R = R′= Me, Et or Ph; R″ = Ph; R″ = Et, Prⁱ or Buⁿ) were prepared and characterised by i.r. and NMR (¹H, ¹³C, ³¹P, ¹⁹⁹Sn) spectroscopy. The NMR data indicate five and six coordinate geometries for [RR′Sn(Cl){SSP(OR″)₂}] and [RR′Sn{SSP(OR″)₂}₂] complexes, respectively. The chloro complexes showed ²J (PSn) whereas such couplings were not observed in the spectra of [RR′Sn{SSP(OR″)₂}₂].     

Synthesis,spectroscopic characterization and in vitro studies of antimicrobial activity of bis(diorganodithiocarbamato)organodithiocarbonatobismuth (III) complexes

A brief account of the synthesis, spectroscopic characterization and the antimicrobial (bacterial and fungal) behaviour of bis(diorganodithiocarbamato)organodithiocarbonatobismuth(III) complexes is presented. The reaction of bis(diorganodithiocarbamato)bismuth(III) chloride with potassium organodithiocarbonate in equimolar ratio yielded the corresponding mixed derivatives of the type [R′₂NCS₂]₂BiS₂COR [where, R′ = CH₃ and C₂H₅; R = Et, Prⁿ, Prⁱ, Buⁿ and Buⁱ]. These have been characterized by molecular weight determinations, melting points (only solid complexes) and elemental (C, H, N, S and Bi) analysis as well as spectral IR and NMR [¹H and ¹³C] studies. The antibacterial and antifungal activities of the free ligands and their bismuth complexes were found in vitro by the disc diffusion method. The complexes showed good antibacterial and antifungal effect on some selected bacterial and fungal strains. The antimicrobial activities of two standard antibiotics (Chloroamphenicol and Terbinafin) were also measured and compared with these complexes. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthetic,spectroscopic, thermal,and structural studies of antimony(III) bis(pyrrolidinedithiocarbamato)alkyldithiocarbonates

An account of the synthesis, spectroscopic, thermal and structural behavior of antimony(III) bis(pyrrolidinedithiocarbamato)alkyldithiocarbonates is presented. The reaction of antimony(III) bis(pyrrolidinedithiocarbamate) chloride with potassium organodithiocarbonate in equimolar ratio yielded the corresponding mixed derivatives of the type [(CH₂)₄NCS₂]₂SbS₂COR [where R = Me, Et, Pr ⁿ , Pr ⁱ , Bu ⁿ , and Bu ⁱ ]. These newly synthesized complexes have been characterized by physicochemical [molecular weight determination, melting points, and elemental analysis], spectral [UV, IR, far-IR, NMR (¹H and ¹³C)], thermal [TG, DTA, and FAB⁺ mass], and structural [powder XRD and SEM] studies. Analytical studies leads to purity and structural properties of the synthesized complexes on the other hand powder X-ray diffraction and SEM studies show that multiphase, polycrystalline, and rod-shaped complexes have been formed having nanorange crystallite size and monoclinic crystal system.     

Photolysis of some unsymmetrical phosphinic azides in methanol: Relative migratory aptitudes of alkyl groups and phenyl in the curtius-like rearrangement

When an alkylphenylphosphinic acid PRhP(O)N₃ (R = Me, Et, Prⁱ, or Bu^t) is photolysed in MeOH either the alkyl or phenyl group can migrate from P to N in the Curtius-like rearrangement. The composition of the product shows that migration of the alkyl group R is preferred. However, the preference is not great and decreases as R changes Bu^t→Prⁱ→Et→Me (approx. migratory aptitudes relative to Ph: 2.1, 1.7, 1.3 and 1.2 respectively), probably because the PhP bond is better able to assume the correct conformation for Ph migration when R is less bulky. For t-butylmethylphosphic azide there is very little preference for migration of Bu^t relative to Me. Small amounts of unrearranged products such as Bu^tPhP(O)NHOMe and Bu^tPhP(O)NH₂ are generally produced in the photolyses, together with the methyl phosphinates RPhP(O)OMe (major product when R = Me) resulting from (non-photochemical) solvolysis of the azide.     

Synthesis,Spectroscopic Studies,and Antifungal Activity of Tris(O-Alkyl or O-Aryltrithiophosphato) Aluminum(III)

Abstract

Aluminum(III) derivatives of O-alkyl or O-aryl trithiophosphate of the type Al[S₂P(SH)OR]₃ (R = Me, Et, Prⁱ, Buⁱ, Ph, CH₂Ph) have been synthesized. The products were obtained as white powdery solids. The monomers are soluble in common organic solvents and were characterized by elemental analyses, molecular weight determinations, and IR and (¹H, ²⁷Al, and ³¹P) NMR spectroscopic studies, which are consistent with six coordinated aluminum and bidentate behavior of the trithiophosphate moiety. The products also exhibit antifungal effectiveness against powdery mildew disease.     

Regiodirected Synthesis and Stereochemistry of 2,4,8‐Trialkyl‐3‐thia‐1,5‐diazabicyclo[3.2.1]octanes and α,ω‐Bis(2,4,6‐trialkyl‐1,3,5‐dithiazinane‐5‐yl)alkanes

2,4,8‐Trialkyl‐3‐thia‐1,5‐diazabicyclo[3.2.1]octanes have been obtained by the regioselective and stereoselective cyclocondensation of 1,2‐ethanediamine with aldehydes RCHO (R═Me, Et, Prⁿ, Buⁿ, Pentⁿ) and H₂S at molar ratio 1:3:2 at 0°C. The increase in molar ratio of thiomethylation mixture RCHO–H₂S (6:4) at 40°C resulted in selective formation of bis‐(2,4,6‐trialkyl‐1,3,5‐dithiazinane‐5‐yl)ethanes. Cyclothiomethylation of aliphatic α,ω‐diamines with aldehydes RCHO (R═Me, Et) and H₂S at molar ratio 1:6:4 and at 40°С led to α,ω‐bis(2,4,6‐trialkyl‐1,3,5‐dithiazinane‐5‐yl)alkanes. Stereochemistry of 2,4,8‐trialkyl‐3‐thia‐1,5‐diazabicyclo[3.2.1]octanes have been determined by means of ¹H and ¹³С NMR spectroscopy and further supported by DFT calculations at the B3LYP/6‐31G(d,p) level. The structure of α,ω‐bis(2,4,6‐trialkyl‐1,3,5‐dithiazinane‐5‐yl)alkanes was confirmed by single‐crystal X‐ray diffraction study.     

Modes of coordination of 1,2-aminothiols in organotin(IV) complexes,as demonstrated by 119Sn, 15N and 13C NMR spectroscopy

Three series of organotin(IV) cysteamine complexes have been prepared in which the 1,2-aminothiol may be monodentate, chelating or bridging, on the ¹¹⁹Sn, ¹⁵N or ¹³C NMR spectroscopic and other physical evidence. Triorganotin(IV) complexes [SnR₃(SCH₂ CH₂NR′₂] (R = Me, Buⁿ or Ph; R′ = H, Me or Et) are monomeric and the aminothiol monodentate in non-coordinating solvents. Dialkyltin(IV) chloro complexes [SnR₂Cl(SCH₂CH₂NR′₂)] (R = Me, Et, Buⁿ or Octⁿ; R′ = H, Me or Et), however, are monomeric with chelation of the aminothiol, like the SnR₂Cl complex of ethyl cysteinate, although nitrogen ligation is hindered by N,N-dialkylation. These solution properties contrast with the polymeric solid structures that are likely for [SnR₂Cl(SCH₂CH₂NH₂)] complexes with R = Me or Et, though not for R = Buⁿ or Octⁿ. Dialkyltin bis-cysteamine complexes [SnR₂(SCH₂CH₂NR′₂)₂] (R = Me, Et, Buⁿ or Octⁿ; R′ = H or Et) show an intermolecular association as neat liquids and in non-coordinating solvents, increasingly with concentration, but again, nitrogen ligation is hindered by tertiary amino groups. The ¹⁵N results usefully complement those from ¹¹⁹Sn and ¹³C NMR spectroscopy.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen der Tetrahalogeno‐bis‐Pyridin‐Osmium(III)‐Komplexe cis‐(n‐Bu4N)[OsCl4Py2] und trans‐(n‐Bu4N)[OsX4Py2], X = Cl,Br

Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Tetrahalogeno‐bis‐Pyridine‐Osmium(III) Complexes cis ‐( n ‐Bu₄N)[OsCl₄Py₂] and trans ‐( n ‐Bu₄N)[OsX₄Py₂], X = Cl, Br By reaction of (n‐Bu₄N)₂[OsX₆], X = Cl, Br, with pyridine and (n‐Bu₄N)[BH₄] tetrahalogeno‐bis‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of cis‐(n‐Bu₄N)[OsCl₄Py₂] ( 1 ) (triclinic, space group P1, a = 9.4047(9), b = 10.8424(18), c = 17.007(2) Å, α = 71.833(2), β = 81.249(10), γ = 67.209(12)°, Z = 2), trans‐(n‐Bu₄N)[OsCl₄Py₂] ( 2 ) (orthorhombic, space group P2₁2₁2₁, a = 8.7709(12), b = 20.551(4), c = 17.174(4) Å, Z = 4) and trans‐(n‐Bu₄N)[OsBr₄Py₂] ( 3 ) (triclinic, space group P1, a = 9.132(3), b = 12.053(3), c = 15.398(2) Å, α = 95.551(18), β = 94.12(2), γ = 106.529(19)°, Z = 2). Based on the molecular parameters of the X‐ray structure determinations and assuming C₂ point symmetry for the anion of 1 and D_2h point symmetry for the anions of 2 and 3 the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants of 1 are in the Cl–Os–Cl axis f_d(OsCl) = 1.58, in the asymmetrically coordinated N′–Os–Cl ^· axes f_d(OsCl ^· ) = 1.45, f_d(OsN′) = 2.48, of 2 f_d(OsCl) = 1.62, f_d(OsN) = 2.42 and of 3 f_d(OsBr) = 1.39 and f_d(OsN) = 2.34 mdyn/Å.     

Intramolecular interaction between ortho-azido and azoxy groups as a new way of forming a N—N bond. Synthesis of 2-alkylbenzotriazole 1-oxides

Heating of 2-(alkyl-NNO-azoxy)-1-azidobenzenes in boiling benzene gave 2-alkyl-benzotriazole 1-oxides (Alk = Me, Et, Prⁱ, and Bu^t). This first-order reaction involves an earlier unknown intramolecular interaction between the azido and azoxy groups with simultaneous release of molecular nitrogen. The cyclization rate increases in the following sequence of the alkyl groups: Me < Et < Prⁱ < Bu^t. Complete assignment of the signals in the ¹H, ¹³C, and ¹⁴N NMR spectra of 2-alkylbenzotriazole 1-oxides was performed. Dedicated to Corresponding Member of the Russian Academy of Sciences E. P. Serebryakov on the occasion of his 70th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 989–996, April, 2005.     

Synthesis and separation of stereoisomeric 2,4,6,8-tetrasubstituted 3,7-dithia-1,5-diazabicyclo[3.3.0]octanes

Heterocyclization of hydrazine with aldehydes R-CHO (R = Me, Et, Prⁿ, Buⁿ, n-C₅H₁₁, Ph, 4-MeOC₆H₄, 3-Py) and H₂S leads to stereoisomeric 2,4,6,8-tetrasubstituted 3,7-dithia-1,5-diazabicyclo[3.3.0]octanes, which were separated by column chromatography. The trans-transoid-trans-configuration of tetramethyl(-ethyl,-propyl)-3,7-dithia-1,5-diazabicyclo-[3.3.0]octanes was inferred from the X-ray diffraction and ¹H and ¹³C NMR spectroscopic data.     

Reactions of Titanium Alkoxides with N-Methylaminoalcohols

N-methylaminoalkoxides of titanium of the type Ti(OR)_4?n(O · CHR′ · CH₂ · NR″R?)_n where R = Et and Pr¹; n = 1–4; and R′ = R″ = H, R? = Me; R′ = H, R″ = R? = Me; R′ = R″ = R? = Me, synthesized by the reactions of titanium alkoxides with aminoalcohols, show interesting variations in their properties like physical state, volatility and molecular complexity. I.r. and p.m.r. spectra of these derivatives have been recorded. A few interchange reactions with methanol and tert-butanol have also been carried out. These aminoalkoxides get cleaved with acetyl chloride and undergo insertion reactions with phenylisocyanate, thus providing the first examples of insertion reactions in such derivatives.     

Nucleophilic addition of alcohols to the C-N multiple bonds of the nitrilium substituent in the anion [2-B10H9(N≡CMe)]−

The reactions of salts of the anion [2-B₁₀H₉(N≡CMe)]⁻ with aliphatic alcohols ROH (R = C _n H_2n+1 (n = 1–6) CH₂CH₂(OEt), Prⁱ, Buⁱ, Bu^t, i-C₅H₁₁) are studied. These reactions result in hydrolytically stable imidates [2-B₁₀H₉{NH=C(OR)Me}]⁻. Their structures were confirmed by the data from mass spectrometry, IR, ¹H, ¹¹B, and ¹³C NMR spectroscopy. The molecular geometry of [2(Z)-B₁₀H₉{NH=C(OBu)Me}]⁻, which formed in nucleophilic addition reaction of n-butyl alcohol to [2-B₁₀H₉(N≡CMe)]⁻, was established by X-ray diffraction analysis.     

1,3,4-Oxa- und 1,3,4-Thia-diphospholane aus Diphosphorsubstituierten 2-Oxa- und 2-Thia-propanen

1,3,4-Oxadiphospholanes and 1,3,4-Thiadiphospholanes from Diphosphorus-substituted 2-Oxa- and 2-Thia-propanes The synthesis of phosphonates and phosphinates of the type (RO)₂(O)PCH₂ZCH₂P(O)(OR)₂, R¹(RO)(O)PCH₂ZCH₂P(O)(OR)₂ and R¹(RO)(O)PCH₂ZCH₂P(O)(OR)R¹ (with Z = O, S; R = Et, Prⁱ; R¹ = Me, Ph) is reported. Acyclic diphosphanes, R¹(H)PCH₂ZCH₂P(H)R² (with Z = O, S; R¹ = R² = H, Me, Ph; R¹ = H, R² = Me), and 1,3,4-Oxadiphospholanes as well as 1,3,4-Thiadiphospholanes are obtained from the esters by reduction.     

Electrooxidation of primary nitramine anions on platinum in MeCN

Oxidation of primary nitramine anions RNNO₂ ⁻Bu₄N⁺ (R=Me, Et, Pr¹, or methoxyfurazanyl) in 0.1N Bu₄NClO₄ in MeCN on a Pt anode was studied by voltammetry and controlled potential electrolysis. It was found that the first stage of oxidation affords the corresponding radicals, which are further stabilized due to hydrogen abstraction from the medium. These radicals are also involved in other reactions, including those, which yield azo derivatives. The possibility of generation of nitrene species in these reactions is discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1935–1939, October, 1999.     

Influence of the cation on the properties of binuclear iron nitrosyl complexes. Synthesis and crystal structure of [Pr4 nN]2[Fe2S2(NO)4]

The binuclear nitrosyl complexes Q₂[Fe₂S₂(NO)₄], where Q=Me, Et, Prⁿ, and Buⁿ, were synthesized. The crystals of [Pr₄ ⁿN]₂Fe₂S₂(NO)₄ were studied by X-ray analysis. The influence of the cation size on the electronic structure and symmetry of its local environment in the synthesized complexes was examined. The decrease in the isomeric shifts in the⁵⁷Fe Mössbauer spectra is related to the increase in the length of the alkyl substituent chain of the quaternary tetraammonium cation and is consistent with changing the structural parameters: a decrease in the bond angle of the Fe?NO bond and stretching vibrations of the NO groups due to changes in intermolecular contacts.