1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe₃N)₄[(dto)₂In(dto)In(dto)₂] ( 1 ), (BzlPh₃P)₄[(dto)₂In(dto)In(dto)₂] ( 2 ), (BzlMe₃N)₃[In(dtsq)₃] ( 3 ), (Bu₄N)₃[In(dtsq)₃] ( 4 ) and (Ph₄P)[In(dtsq)₂(DMF)₂] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P2₁/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P2₁/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.     

Synthesis and Characterisation of N,N′-Disubstituted 1,2-phenylenebis(amido)tin(II) Compounds; X-Ray structures of 1,2- and of [1,2- (tmeda)

Cyclic bis(amido)tin(II) compounds 1,2- [R = SiMe₃] ( 4 ), SiMe₂Bu^t ( 5 ) and CH₂Bu^t ( 6 )], as well as ( 4 )₂(μ-tmeda) 7 have been obtained either from (i) the corresponding dilithium compound 1,2-C₆H₄[N(R)Li]₂ 1–3 and SnCl₂ for 4–6 , respectively, (or for 4 ) 2 1 + [Sn(μ-Cl){N(SiMe₃)₂}]₂; or (ii) 1,2-C₆H₄[N(H)R]₂ + Sn[N(SiMe₃)₂]₂ for 4–6 ; or for 7 from 4 and tmeda. Compounds 4–6 are monomeric, yellow, thermochromic (becoming redder on heating), diamagnetic, crystalline and are lipophilic and sublimable in vacuo. Compound 7 is colourless. The molecular structures of 6 and 7 have been determined from single crystal X-ray diffraction data. Compound 6 crystallises in bimolecular aggregates, in which there is a weak η-C₆ … Sn contact.     

Titanium(III) and vanadium(III) chloride complexes with 2-pyridylphenylacetonitrile and 1,2-dicyano-1,2-diphenyl-1,2-di(2′-pyridyl)ethane

Summary 2-Pyridylphenylacetonitrile (ppa) and 1,2-dicyano-1,2-diphenyl-1,2-di(2-pyridyl)ethane (dcppe) react with titanium(III) and vanadium(III) chlorides yielding complexes of formulae: [TiCl₃(ppa)₂], [TiCl₃(ppa)₃], [VCl₃(ppa)], [TiCl₃(dcppe)] and [(VCl₃)₂(dcppe)]. The results obtained suggest pentacoordinated structures for complexes, except for [TiCl₃(ppa)₃] where an hexacoordinated stereochemistry around the metal is proposed.     

Chiral functionalized bisphosphine ligands: Transition metal complexes of 1,2-bis(tert-Butylchlorophosphino)-1,2-dicarba-closo-dodecaborane(12)

When rac- or meso-1,2-bis(tert-butylchlorophosphino)-1,2-dicarba-closo-dodecaborane(12) (1a or 1b) is reacted with [M(CO)₄(NBD)] (M = Cr, Mo, NBD = norbornadiene), [Mo(CO)₄(EtCN)₂] or [W(CO)₆], rac-[Cr(CO)₄{1,2-(P^tBuCl)₂C₂B₁₀H₁₀}] (2), rac- or meso-[Mo(CO)₄{1,2-(P^tBuCl)₂C₂B₁₀H₁₀}] (3a or 3b) and rac-[W(CO)₄{1,2-(P^tBuCl)₂C₂B₁₀H₁₀}] (4) could be isolated as pure diastereomers. UV irradiation of 1 with [Cr(CO)₆] in moist THF proceeds with hydrolysis and formation of [Cr(CO)₄{1,2-(P(OH)^tBu)₂C₂B₁₀H₁₀}] (5) which contains the metal complex-stabilized phosphinous acid. Compounds 2–5 were characterized spectroscopically (¹H, ³¹P, ¹¹B, ¹³C NMR), by mass spectrometry and by X-ray structure determination.     

Reactions of 2-pyridylphenylacetonitrile and 1,2-dicyano-1,2-diphenyl-1,2-di(2-pyridyl)ethane with cobalt(II), nickel(II), copper(II) and zinc(II) chlorides and copper(II) bromide

Summary 2-Pyridylphenylacetonitrile (ppa) is oxidized by copper(II) halides in 1,2-dichloroethane to 1,2-dicyano-1,2-diphenyl-1,2-di(2-pyridyl)ethane (dcppe), yielding 41 complexes of dcppe with copper(II) dihalide, [CuX₂(dcppe)₄] (green). Nickel(II) and zinc(II) chlorides react with ppa giving complexes of a general formula [MCl₂(ppa)₂].Dcppe reacts with copper(II), zinc(II) chlorides and copper(II) bromide yielding complexes of formulae [CuCl₂(dcppe)₄] (yellow), [ZnCl₂(dcppe)₂] and [CuBr₂(dcppe)]. No reaction is observed with cobalt(II) and nickel(II) chlorides.     

1,2‐Bis­(methylsulfanyl)‐1,2‐dicarba‐closo‐dodecaborane(12)

In the title compound, 1,2‐(SCH₃)₂‐1,2‐closo‐C₂B₁₀H₁₀ or C₄H₁₆B₁₀S₂, the methylsulfanyl groups are bonded to the C atoms of the 1,2‐dicarba‐closo‐dodecaborane cage. The C_cage—C_cage distance is 1.8033 (18) Å and the S—C_cage—C_cage—S torsion angle is 1.07 (13)°. The C_cage—C_cage distance is compared with those in other 1,2‐dicarba‐closo‐dodecaborane derivatives.     

Bis(1,2‐diselenoquadratato)metallate

Bis(1,2‐diselenosquarato) Metalates A series of 1,2‐diselenosquarato metalates [M(dssq)₂]^2– (M = Pd²⁺, Pt²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Cd²⁺, Pb²⁺, VO²⁺) was available by direct synthesis from the appropriate metal salt with dipotassium 1,2‐diselenosquarate in deoxygenized water under an argon athmosphere. The copper(II)complex, [Cu(dssq)₂]^2–, and the oxovanadium(IV)complex, [VO(dssq)₂]^2–, were identified in solution by EPR spectroscopy (parameters: [Cu(dssq)₂]^2–: g₀ = 2.073; a = –76.0 · 10^–4 cm^–1, a = 47.0 · 10^–4 cm^–1; [VO(dssq)₂]^2–: g₀ = 1.986; a = 74.9 · 10^–4 cm^–1). The complexes bis(tetraphenylphosphonium)[bis(1,2‐diselenosquarato)nickelate(II)], (Ph₄P)₂[Ni(dssq)₂], and bis(tetraphenylphosphonium)[bis(1,2‐diselenosquarato)zincate(II)], (Ph₄P)₂[Zn(dssq)₂], were characterized by X‐ray structure analysis. The square‐planar Ni^II complex (Ph₄P)₂[Ni(dssq)₂] crystallizes in the monoclinic spacegroup P2₁/n with the unit cell parameters a = 11.1472(8) Å, b = 15.331(1) Å, c = 14.783(1) Å, β = 94.441(1)° and Z = 2. The Zn^II‐complex (Ph₄P)₂[Zn(dssq)₂] is tetrahedral coordinated and crystallizes in the monoclinic spacegroup P2₁/c with the unit cell parameters a = 9.4238(1) Å, b = 18.5823(3) Å, c = 29.5309(5) Å, β = 96.763(1)° and Z = 4.     

Reactions of 2-pyridylphenylacetonitrile and 1,2-dicyano-1,2-di(phenyl)-1,2-di(2-pyridyl)ethane with titanium(IV), vanadium(IV), chromium(III) and iron(III) chlorides

Summary 2-Pyridylphenylacetonitrile (ppa) is oxidized by iron(III) chloride in dry ethanol to 1,2-dicyano-1,2-di(phenyl)-1,2-(2-pyridyl)ethane (dcppe). When 1,2-dichloroethane or ether are used as solvents, a 31 complex of dcppe with iron trichloride, [(FeCl₃)₃(dcppe)] is obtained.Titanium(IV), vanadium(IV) and chromium(III) chlorides react with ppa and dcppe, giving complexes of general formulae [MCl₄(ppa)] (M = Ti or V), [CrCl₃(ppa)_n] (n = 2 or 3), [(MCl₄)₂(dcppe)] (M = Ti or V) and [CrCl₃(dcppe)].     

Über Chalkogenolate. 160. Umsetzung von 1,2-Ethandithiolaten mit Kohlenstoffdisulfid 2. 1,2-Ethan-bis(trithiokohlensäure) und Alkylester der Säure

On Chalcogenolates. 160. Reaction of 1,2-Ethanedithiolates with Carbon Disulfide. 2. 1,2-Ethane-bis(trithiocarbonic acid) and Alkyl Esters of This Acid The reaction of potassium 1,2-ethane-bis(trithiocarbonate) with hydrochloric acid at 0°C gives unstable, deep yellow coloured 1,2-ethane-bis(trithiocarbonic acid) The 1,2-ethane-bis(alkyl trithiocarbonates) RS? CS? SCH₂CH₂S? CS? SR, where R = CH₃ and C₂H₅, have been formed by reaction of potassium 1,2-ethane-bis(trithiocarbonate) with the corresponding alkyl iodide. The called compounds have been characterized by means of diverse spectroscopic methods.     

First synthesis of (1,2-C2)-monolignol glucosides

The monolignol glucosides (1,2-¹³C₂)-p-glucocoumaryl alcohol, (1,2-¹³C₂)-coniferin and (1,2-¹³C₂)-syringin, and the glucosides of (1,2-¹³C₂)-p-coumaric, (1,2-¹³C₂)-ferulic and (1,2-¹³C₂)-sinapic acids were synthesized by condensation of the corresponding aldehydes with (1,2,3-¹³C₃)-malonic acid. The free acids were converted to the acyl chlorides prior to their reduction to alcohols.     

Synthesis and characterization of three dinuclear copper(I) complexes of 1,2‐bis(diphenylphosphino)‐1,2‐dicarba‐closo‐dodecaborane

Three dinuclear copper(I) complexes, [Cu₂(µ‐Cl)₂(1,2‐(PPh₂)₂‐1,2‐C₂B₁₀H₁₀)₂]·2CH₂Cl₂ ( 1 ), [Cu₂(µ‐Br)₂(1,2‐(PPh₂)₂‐1,2‐C₂B₁₀H₁₀)₂]·2THF ( 2 ) and {Cu₂(µ‐I)₂[1,2‐(PPh₂)₂‐1,2‐C₂B₁₀H₁₀]₂} ( 3 ) have been synthesized by the reactions of CuX (X = Cl, Br and I) with the closo ligand 1,2‐(PPh₂)₂‐1,2‐C₂B₁₀H₁₀. All these complexes were characterized by elemental analysis, FT‐IR, ¹H and ¹³C NMR spectroscopy and X‐ray structure determination. Single crystal X‐ray structure determinations show that every complex contained di‐µ‐X‐bridged structure involving a crossed parallelogram plane formed by two Cu atoms and two X atoms (X = Cl, Br, I). The geometry at the Cu atom was a distorted tetrahedron, in which two positions were occupied by two P atoms of the PPh₂ groups connected to the two C atoms of carborane (Cc), and the other two resulted from two X atoms which bridged the other Cu atom at the same time. To the best of our knowledge, this is the first example of copper(I) complexes with 1,2‐diphenylphosphino‐1,2‐dicarba‐closo‐dodecaborane as ligand characterized by X‐ray diffraction. The catalytic property of the complex 3 for the amination of iodobenzene with aniline was also investigated. Copyright © 2005 John Wiley & Sons, Ltd.     

(1R,2R)‐1,2‐Di­phenyl‐1,2‐bis(8‐quinoline­sulfonyl­amino)ethyl­enedi­amine–acetone (1/1)

The crystal structure of the new chiral complex (1R,2R)‐1,2‐di­phenyl‐1,2‐bis(8‐quinoline­sulfonyl­amino)‐ ethyl­enedi­amine–acetone (1/1), C₃₂H₂₆N₄O₄S₂^.C₃H₆O, is reported. The conformation of the C₃₂H₂₆N₄O₄S₂ (BQSDA) mol­ecule is determined by a bifurcated N—H?N hydrogen‐bond system. The acetone of solvation is linked to the BQSDA mol­ecule by an N—H?O hydrogen bond.     

Koordinationseigenschaften von Carbaboranylchlorophosphanen: Synthese und Molekülstruktur von cis-rac-Molybdäntetracarbonyl{1,2-bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaboran(12)}

Coordination Properties of Carbaboranylchlorophosphines: Synthesis and Molecular Structure of cis-rac -Molybdenumtetracarbonyl{1,2-bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaborane(12)} Rac-1,2-bis(chlorophenylphosphino)-1,2-dicarba-closo-dodecaborane(12) ( 1 ) reacts with [Mo(CO)₄(NBD)] (NBD = norbornadiene) after several hours at 50–55 °C to yield cis-rac-[Mo(CO)₄{1,2-(PPhCl)₂C₂B₁₀H₁₀}] ( 2 ). 2 was characterised spectroscopically (¹H, ¹³C, ¹¹B and ³¹P NMR) and by crystal structure determination.     

1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolan und 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborin: Synthese und Struktur sowie Berechnungen zur Molekülstruktur

1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane and 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine: Synthesis and Structure as well as Calculations on the Molecular Structure The diphosphides K₂[(C₆H₅)P? (C₆H₅)P? P(C₆H₅)], 4 or K₂[(tBuP)? (tBuP)₂? P(tBu)], 5 , react with (ClBNMe₂)₂ to form the binary 5-membered ring system 1,2-bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane (C₆H₅P)₃(BNMe₂)₂, 2a , and the 6-membered ring system 1,2-bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine, (tBuP)₄(BNMe₂)₂, 3a , respectively. 2a and 3a could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analyses. The two ring systems are folded; 2a exists in the ?envelope”?- 3a in the ?boat”?-conformation. Ab initio computations for 3,4,5-triphospha-1,2-diborolane M5 show that the global minimum is characterized by one B? P double bond. The parent compound geometry M6 is characterized by transannular bonding in the PH? BH? BH? PH moiety which differs in character from those in the four- and five-membered rings (BH)₂(PH)₂ and (BH)₂(PH)₃ M5 d , respectively. Explicit calculation of the influence of amino substituents on boron improved agreement of the bond length between computed and X-ray data.     

Herstellung,Kristallstruktur und magnetische Eigenschaften von Bis (1,2-benzochinondiimid)-1,2-benzosemichinondiimidokobalt (II)-tetraphenylborat-pentahydrat

Synthesis, Crystal Structure, and Magnetic Properties of Bis(1,2-benzoquinonediimide)-1,2-benzosemiquinonediimidocobalt (II)-tetraphenylborate-pentahydrate Co (II)-salts catalyze the autoxidation of 1,2-diaminobenzene in slightly alkaline solution. Deeply coloured metal complexes are formed during the reaction suggesting intermediate radical or semiquinonediimide stages of the aromatic ligands. Starting from [Co^II (1,2-diaminobenzene)₃] (ClO₄)₂ two different intermediate complexes can be isolated, the magnetic properties of which point to a high-spin cobalt (II)-complex and a low-spin cobalt (II)-complex with a radical ligand respectively. The X-ray structure determination of the latter complex yielded a square pyramidal arrangement, the Co-N₄-plane distance being only 0.5 Å. The dark blue coloured complex is diamagnetic. Two of the aromatic ligands have the oxidation state of a benzoquinonediimide while the third, coordinated by one amino group only, is pseudosemiquinonoid. Crystals of C₄₂H₄₈BCoN₆O₅ are monoclinic, a = 14.493 (5), b = 18.341 (7), c = 15.492 (5) Å, β = 99.198 (5), space group P2¹/n. D_obs. = 1.290, D_calc. = 1.289 g/cm³ for Z = 4. The structure was solved by Patterson's method and refined by least-squares techniques to R = 0.088 for 2866 of 5014 independent reflexions.     

Synthesis of 1,2-bis(methoxyamino)cycloalkanes from alicyclic 1,2-bis(hydroxyamines)

Derivatives of 1,4-dihydroxypiperazine-2,3-dione were obtained by reaction of cis-1,2-bis(hydroxyamino)cycloalkanes with diethyl oxalate. Their alkylation with CH₂N₂ or Mel afforded 1,4-dimethoxypiperazine-2,3-diones. Hydrolysis of the latter gave 1,2-bis(methoxyamino)cycloalkanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–929, April, 1996.     

Spectroscopic studies of new Co(II), Cu(II), and Ni(II) complexes with 1,2-Bis(<Emphasis Type="Italic">m</Emphasis>-aminophenoxy)ethane

1,2-Bis(m-aminophenoxy)ethane was prepared in a one-stage process. In this reaction, Pd/C was used as a catalyst. 1,2-Bis(m-aminophenoxy)ethane was synthesized from 1,2-bis(m-nitrophenoxy)ethane. Diamine complexes [CoLCl₂], [CuLCl₂] and [NiL₂]Cl₂ have been synthesized and characterized by elemental analyses, Λ_M, IR, UV-Vis, ¹H NMR and magnetic measurements.     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

Crystal structure and photoreactivity of a halogen‐bonded cocrystal based upon 1,2‐diiodoperchlorobenzene and 1,2‐bis(pyridin‐4‐yl)ethylene

The formation of a photoreactive cocrystal based upon 1,2‐diiodoperchlorobenzene ( 1,2‐C₆I₂Cl₄ ) and trans‐1,2‐bis(pyridin‐4‐yl)ethylene ( BPE ) has been achieved. The resulting cocrystal, 2( 1,2‐C₆I₂Cl₄ )·( BPE ) or C₆Cl₄I₂·0.5C₁₂H₁₀N₂, comprises planar sheets of the components held together by the combination of I…N halogen bonds and halogen–halogen contacts. Notably, the 1,2‐C₆I₂Cl₄ molecules π‐stack in a homogeneous and face‐to‐face orientation that results in an infinite column of the halogen‐bond donor. As a consequence of this stacking arrangement and I…N halogen bonds, molecules of BPE also stack in this type of pattern. In particular, neighbouring ethylene groups in BPE are found to be parallel and within the accepted distance for a photoreaction. Upon exposure to ultraviolet light, the cocrystal undergoes a solid‐state [2 + 2] cycloaddition reaction that produces rctt‐tetrakis(pyridin‐4‐yl)cyclobutane ( TPCB ) with an overall yield of 89%. A solvent‐free approach utilizing dry vortex grinding of the components also resulted in a photoreactive material with a similar yield.     

Electrochemical synthesis of halogen derivatives of bis(1,2-dicarbollyl)cobalt(III)

A convenient electrochemical method for the synthesis of 8,8-dihalogen derivatives of bis(1,2-dicarbollyl)cobalt(III) anion [8,8X₂-3,3-Co(1,2-C₂B₉H₁₀)]^– (X = Cl, Br, I) was developed. The method includes the electrolysis of a solution of alkaline metal halide and tetramethylammonium salt of bis(1,2-dicarbollyl)cobalt(III) in methanol at 50 °C in a one-compartment electrochemical cell with a nickel cathode and platinum anode.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2448–2451, November, 2004.