Synthesis and structure of bismuth complexes [Ph4P]4[Bi8I28], [Ph4P]2[Bi2I8·2Me2S=O]·2Me2S=O, [(Me2S=O)8Bi][Bi2I9]

Complexes [Ph₄P]₂[Bi₂I₈(Me₂S=O)₂]·2Me₂S=O (I) and [Ph₄P]₄[Bi₈I₂₈] (II) were obtained by the reaction of tetraphenylphosphonium iodide with bismuth triiodide in DMSO and acetone, respectively. Dissolving bismith iodide in DMSO resulted in the formation of complex [(Me₂S=O)₈Bi][Bi₂I₉] (III). Reactions of complexes II or III with tetraphenylphosphonium iodide in DMSO yielded complex I. The structure of the obtained bismuth complexes was confirmed by X-ray diffraction data.     

Synthesis,Structure and Properties of C(X)NHP(Y) Fragment Containing Compounds

Abstract

N-(thio)carbonyl(thio)amidophosphate, their open-chain and crown-containing analogues with a C (X) NHP (Y) fragments are associated with intermolecular hydrogen bonds as C=X…H-N and P=Y…H-N or intramolecular hydrogen bonds of N-H…O(macrocycle). These compounds easily enter into alkylation reaction, are added according to C=N bonds of activated imines, take part in O → S and S → O exchanging reactions.     

INORGANIC RINGS WITH GALLIUM ORGANYLS AND IMINODIPHOSPHINECHALCHOGENIDES

The organometallic complexes of general formula [Me ₂ Ga{(XPR ₂ ) (YPR′ ₂ )N}] (R, R′ = Ph, X, Y = O, (1); R, R′ = Ph, X, Y = S (2); R, R′ = Ph, X = O, Y = S (3); R = Me, R′ = Ph, X = O, Y = S (4)) were obtained by alkane eliminations from Me ₃ Ga and the free acidic ligands, LH, in toluene solutions. Complexes 1– 4 seem to be potential precursors to cationic gallium species.     

Synthesis and crystal structure of tetraphenylphosphonium isocyanurate pentahydrate

A new complex [Pb(Crypt-222)(H₂O)₂]⁺ · 2(iso-PrO)₂P(S)N⁻C(S)Ph (I) was prepared and studied by X-ray diffraction: space group C2/c, a = 16.170 ?, b = 10.405 ?, c = 34.116 ?, β = 103.32°, Z = 4. The monoclinic structure of I was solved by direct methods and refined by full-matrix least-squares calculation in the anisotropic approximation to R = 0.098 for 6414 independent reflections (CAD4 automated diffractometer, λMoK _α). In structure I, the host-guest [Pb(Crypt-222)(H₂O)₂]⁺ cation is located on a twofold crystallographic axis. The Pb²⁺ cation is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and by two O atoms of water molecules. The Pb²⁺ coordination polyhedron (CN = 10) is a highly distorted two-base-centered dicapped trigonal prism. The crystal structure of I contains one independent thiophosphoramidate anion with deprotonated nitrogen. In crystal I, the complex cation is connected to two thiophosphoramidate anions by ion-ion hydrogen bonds, O(w)-H...S.     

SYNTHESIS AND PROPERTIES OF THE FIRST DISULFUR AND DISELENIUM COMPLEXES OF PLATINUM

The reactions of overcrowded platinum(0) complexes [Pt{P(Ar)Me₂}₂] (Ar = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt), 2,6-bis[bis- (trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt)) with elemental sulfur and selenium resulted in the formation of the first platinum disulfur and diselenium complexes, [Pt(S₂){P(Ar)Me₂}₂] (4a (Ar = Tbt), 4b (Ar = Bbt) and [Pt(Se₂){P(Ar)Me₂}₂] (5a (Ar = Tbt), 5b (Ar = Bbt)) respectively. The x-ray crystallographic analyses of 4b and 5b showed a novel three-membered PtE₂ (E = S, Se) ring structure with a square planar geometry around the platinum center. The oxidation of 4b and 5b with an equimolar amount of m-chloroperbenzoic acid or tert-butyl hydroperoxide in dichloromethane yielded the corresponding disulfur and diselenium monoxide complexes [Pt(E₂O){P(Bbt)Me₂}₂] (6 (E = S), 7 (E = Se)). The further reactions of 6 and 7 with an excess of oxidants gave the corresponding O,S-coordinated thiosulfato complex [Pt(S₂ O₃){P(Bbt)Me₂}₂] (8) and the O,O-coordinated selenito complex [Pt(SeO₃){P(Bbt)Me₂}₂] (11), respectively. The dynamic behavior in solution was revealed by the variable-temperature NMR spectroscopy for 4b, 5b, 8, and 11, which indicates the existence of the intramolecular CH···E (E = O, S, Se) interactions between the methine hydrogens of the o-bis(trimethylsilyl)methyl groups and the Pt-bonded chalcogen atoms.     

Metal Coordinated Phosphinite Derivatives

Abstract

The following phosphinites as derivatives of the unknown diphenylphosphinous acid with phosphorus(III) of the type (C₆H₅)₂POX (X=H, NH₄, S(O)R, P(C₆H₅)₂) are normally unstable in the free state. However, they can be stabilized in the protecting coordination sphere of transition metal complexes by building them up by direct or indirect methods. The simple starting molecule is, in principle, diphenylphosphane, (C₆H₅)₂PH, which can be functionalized by oxidation or coordination and subsequent substitution and reduction reactions as it is shown in the following scheme:     

Complexes of Co(II) and Zn(II) with N-(Thio)phosphorylthioureas AdNHC(S)NHP(O)(OiPr)2 and MeNHC(S)NHP(S)(OiPr)2

The reaction of the potassium salt of the N-(thio)phosphorylated thioureas AdNHC(S)NHP(O)(OiPr)₂ (HL^I , Ad = Adamantyl) and MeNHC(S)NHP(S)(OiPr)₂ (HL^II ) with Co(II) and Zn(II) in aqueous EtOH leads to [ML^I,II ₂] chelate complexes. They were investigated by UV-vis, ¹H and ³¹P NMR spectroscopy, and microanalysis. The molecular structures of [ML^I ₂] were elucidated by single crystal X-ray diffraction analysis. The metal centers in both complexes are found to be in a distorted-tetrahedral O₂S₂ environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated L^I ligands. The photoluminescence properties of [ZnL^II ₂] are also reported.     

Synthesis,characterization, structures,and DFT study of zinc(II) complexes with tributylphosphine chalcogenides

Four new zinc(II) complexes of the type [ZnCl₂(n-Bu₃PE)₂] (E=O (1), S (2), Se (3), or Te (4)) have been synthesized from zinc(II) chloride and the ligands n-Bu₃PE giving yields of 56–88%. The adducts were characterized by multinuclear (³¹P, ¹³C, and ⁷⁷Se) NMR, conductivity, IR spectroscopy and by X-ray analyses. Zinc complexes 1–4 are compriseS of two ligands coordinated to the metal center in a distorted tetrahedral arrangement. The P=E bond lengths of 1.497(7) (E=O), 2.000(4) (E=S), and 2.178(2) Å (E=Se) in these complexes are slightly elongated compared to those in the free ligand. In addition, a DFT/B3LYP theoretical study on the geometry optimization of the title ligands and their zinc complexes has been carried out in order to support and complement the experimental data and to further investigate the nature of the chalcogenide-metal interaction. The results show good agreement between the experimental and theoretical data.     

Umsetzung von 2-Dimethylamino-(1,3,2)-diox-, oxathi- und dithi-arsolanen mit Alkoholen und Thiolen

Reaction of 2-Dimethylamino-(1,3,2)-diox-, oxathi-, and dithi-arsolanes with Alcohols or Thiols The reactions of 2-dimethylamino-(l, 3,2)-diox-, oxathi- and dithi-arsolanes (CH₂)₂XYAs? N(CH₃)₂ (X = Y = O or S; X = S, Y = O) with alcohols and thiols yield by cleavage of the As? N bond in the formation of alkoxy and alkylmercaptoarsolanes (CH₂)₂XYAs? ZR (X = Y = Z = O or S; X = Y: O, Z = S; X = Y = S, Z = O; X = S, Y = O, Z = O or S), respectively. Some of these arsolanes are not stable but rearrange under formation of 1,2-Bis-(arsolanyl)ethane and arsinous acid esters.     

四个基于酰腙配体的双核苄基锡配合物的合成、晶体结构及体外抗癌活性

通过微波"一锅法"合成了4个双核苄基锡配合物:{[C_4H_3S(O)C=N-N=C(Me)COO](PhCH_2)_2Sn(MeOH)}_2(C1)、{[C_4H_3S(O)C=NN=C (Me)COO](p-Cl-C_6H_4CH_2)_2Sn (MeOH)}_2(C2)、{[C_4H_3S (O)C=N-N=C (PhCH_2)COO](PhCH_2)_2Sn (MeOH)}_2(C3)、{[C_4H_3S (O)C=N-N=C(PhCH_2)COO](p-Cl-C_6H_4CH_2)_2Sn(MeOH)}_2(C4),利用元素分析、IR、~1H NMR、~(13)C NMR、~(119)Sn NMR、HRMS以及X射线单晶衍射等表征了配合物结构。4个配合物分子均为双锡核分子,以Sn_2O_2四元环为中心对称,且中心锡原子与配位原子形成七配位畸变五角双锥构型。测试了配合物C1～C4的热稳定性以及配合物对癌细胞H460、HepG2、MCF7的体外抑制活性,结果表明:配合物C2是4个新合成的配合物中抑制癌细胞效果最好的化合物。     

P-Chiral Thioxaphosphoranesulphenyl Chlorides RR1 P(S)SC1. A New Tool in Stereochemistry of Organophosphorus-Sulphur Compounds

Abstract

Phosphoranesulphenyl halides of the general formula RR'P(Y)SX and their selenium analogues RR'P(Y)SeX (X=Cl,Br; Y=O,S) have been shown to be useful intermediates for access to many new classes of compounds con-taining phosphorus, sulphur, or selenium centers.'     

Generation and characterization of ionic and neutral [HS-P-OH]<Superscript>+/·</Superscript> and S=P(OH)<Stack><Subscript>2</Subscript><Superscript>+/·</Superscript></Stack> in the Gas Phase by Tandem Mass Spectrometry and Computational Chemistry

Dissociative electron ionization of diethyl dithiophosphate (I) and O,O′-diethyl methylphosphonothioate (II) generates moderately abundant m/z 81 ions of composition [P, O, S, H₂]⁺. From tandem mass spectrometry experiments and theoretical calculations at the B3LYP/6-31G(d,p), G2, and G2 (MP2) levels it is concluded that the majority of the ions have the structure of HS-P-OH⁺ (1a ⁺) and it is separated by high-energy barriers from its isomers P(= S)OH₂⁺ (1b ⁺), P(= O)SH₂⁺ (1c ⁺), HP(= S)OH⁺ (1d ⁺), and HP(= O)SH⁺ (1e ⁺). Low-energy (metastable) ions 1a ⁺ dissociate via losses of H₂O and H₂S to yield m/z 63 (PS⁺) and m/z 47 (PO⁺) product ions, respectively. These reactions involve isomerization of 1a ⁺ into the stable isomers 1b ⁺ and 1c ⁺. Neutralization-reionization experiments confirm the theoretical prediction that radical 1a ^· is a stable species in the gas-phase. Variable-time NR experiments indicated that only a small fraction of metastable 1a ^· radicals dissociate in the 0.4–4.6 μs time window, while most dissociations occurred on a shorter time scale. RRKM calculations were performed to investigate unimolecular dissociation kinetics of 1a ^· which were found to be in agreement with the fragmentation observed in the NR spectrum. The 70-eV electron ionization of (I) and diethyl chlorothiophosphate (III) yields m/z 97 ions, predominantly of the structure S = P(OH)₂⁺ (2a ⁺). This conclusion follows from tandem mass spectrometry experiments and theoretical calculations. The calculations predict that (2a ⁺) is separated by high-energy barriers from its isomers O = P(SH)OH⁺ (2b ⁺), S = P(= O)OH₂⁺ (2c ⁺), and O = P(= O)SH₂⁺ (2d ⁺). Neutralization-reionization experiments confirmed that 2a ^· radical is a kinetically stable species on the time scale of up to 5 μs, which is in agreement with ab initio calculations. However, owing to a mismatch of Franck-Condon factors a large fraction of 2a ^· dissociates by loss of SH^· yielding O=P-OH.     

Synthesis and vibrational spectra of copper(II) and erbium(III) complexes with 2-[2′-(oxymethyldiphenylphosphinyl)phenyldiazenyl]-4- tert -butylphenol (HL) [CuL2] · 2H2O and Er(NO3)2 · 2 HL · 2H2O. Crystal structure of [CuL2] · 2H2O

The syntheses of the complex copper salt CuL₂ · 2H₂O (I) and the erbium nitrate complex Er(NO₃)₃ · 2HL · 2H₂O (II) (HL is 2-[2′-(oxymethyldiphenylphosphinyl)phenyldiazenyl]-4-tert-butylphenol) have been described. Basic vibrational frequencies in the IR spectra of I and II have been interpreted. The crystal structure of I has been determined by X-ray crystallography: the crystals are monoclinic, a = 15.157(3) ?, b = 17.080(2) ?, c = 22.451(9) ?, β = 106.09(3)°, V = 5584(3) ?³, Z = 4, space group C2/c, R = 0.0546 (for 1152 reflections with I > 2σ(I)). The coordination polyhedron of the copper atom (symmetry C ₂) can be described as a symmetrically elongated square bipyramid (4+2). The basic square of the Cu polyhedron is formed by the oxygen atom of the substituted phenol and one of the nitrogen atoms of the azo group of each of the two deprotonated ligands L⁻ (Cu-N, 1.969(6) ?; Cu-O, 1.899(5) ?). The angles between the opposite O and N atoms are 157.6°, and the other equatorial angles are in the range 90.6°–95.9°. The axial positions are occupied by the anisole O(2) and O(2A) atoms (Cu-O, 2.737(6) ?, the O(2)Cu(1)O(2A) angle, 132.3°). In the crystal of I, complex molecules and water molecules of crystallization are combined by a system of hydrogen bonds. IR spectra show that, in complex II, as distinct from compound I, the HL ligand is coordinated to the erbium atom through the phosphoryl oxygen atom. Original Russian Text ? A.Yu. Tsivadze, L.Kh. Minacheva, I.S. Ivanova, V.E. Baulin, E.N. Pyatova, V.S. Sergienko, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 4, pp. 601–607.     

SYNTHESIS AND DESULFURATION OF THIANAPHTHEN-3-CARBOXYLIC ACID DERIVATIVES

Abstract

Bis(trimethylsilyl)peroxide (BSPO) can be used for chemo- and stereoselective generation of P=O group by oxygenation of P(III) centre and transformation of P=S and P=Se groups.     

New heteroorganic betaines containing the (+)E15—C—E14—X(–) and (+)E15—C—E14(–) structural fragments (E15 = P,As; E14 = Si,Ge, Sn; X = C,S, O,NR)

The review surveys the data on the reactions of phosphorus and arsenic ylides with compounds containing E=X bonds (E = C, Si, Ge, or Sn; X = C or S), cyclic oligomers (R₂ES)_n (n = 2 or 3), and heavier analogs of carbenes. These reactions give rise to two new classes of heteroorganic betaines containing the ⁽⁺⁾E¹⁵—C—E¹⁴—X^(–) (I) and ⁽⁺⁾E¹⁵—C—E^14(–) (II) (E¹⁵ = P or As; E¹⁴ = Si, Ge, or Sn; X = C or S) structural fragments. Procedures for the synthesis of these compounds, their reactivities, the X-ray diffraction structures, and the electronic structures established by high-level quantum-chemical calculations are considered in detail. The carbon analogs of betaines of type I, viz., compounds bearing the ⁽⁺⁾P—C—C—X^(–) fragment (III), are also discussed. The latter were long considered as possible intermediates in the reactions of compounds containing the polar C=X bond (X = C, O, S, NR, etc.) with phosphorus ylides (classical Wittig and Corey—Chaykovsky reactions and related processes).     

CRYSTAL STRUCTURE OF THE NOVEL COMPOUND (1α, 3bT, 5α)-1,3-DIPHENYL-5-HYDRIDO-5-ISOPROPOXY-1λ6, 3λ6,2,4,6,5λ5-DITHIATRIAZAPHOSPHORINE-1,3-DIOXIDE. A COMPARISON WITH RELATED STRUCTURES

Abstract

The title compound (1α, 3β, 5α)-(NSOPh)₂NP(H)O-i-Pr crystallizes in the spacegroup P2₁/n with cell dimensions: a = 12. 150(2), b = 8.911(1), c = 17.614(3) Å, β = 107.52(1)^o; Z = 4. The structure was solved by direct methods and refined by least-squares techniques to an R value of 0.048 for 2420 independent reflections (collected at room temperature) with I > 2.5 σ(I). The unit cell contains dimeric units which are formed by unprecedented P[sbnd]H…O[dbnd]S bridges. The conformation of the inorganic ring skeleton can be described as a boat; phosphorus and sulfur atoms show a distorted tetrahedral geometry. The S[sbnd]N bond lengths differ slightly, ranging from 1.547(3) to 1.588(2) Å. The exocyclic bond lengths are P[sbnd]H = 1.34(2), P[sbnd]O = 1.553(2), S[sbnd]O = 1.439(2) (mean value), and S[sbnd]C = 1.767(4) (mean value) Å. From a comparison with analogous structures the degree of asymmetry (ΔI = {[P[sbnd]N]-[S[sbnd]N]}Å) in the SNP unit is related to the difference in electronegativity between the sulfur and phosphorus centres.     

New Organophosphorus Proligands and Amide Precursors: Crystal and Molecular Structures of Ph2P(X)NH(C6H3Pri 2-2,6) (X = O,S) and (OPPh2)(O2SMe)N(C6H3Pri 2-2,6)

The new organophosphorus proligand (OPPh₂)(O₂SMe)NR (R = C₆H₃Prⁱ ₂–2,6) (3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph₂P(O)NR] with MeSO₂Cl in a 1:1 molar ratio. The precursor Ph₂P(O)NHR (1), as well as its thio analogue Ph₂P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (¹H, ¹³C, and ³¹P) NMR spectroscopy. The molecular structures of 1–3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N–H···X (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn–syn conformation of the O?P(C)₂–N–S(C)(?O)₂ skeleton.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

THEORETICAL COMPARISON OF THE BONDING OF CHALCOCARBONYL LIGANDS

Abstract

Fenske-Hall molecular orbital calculations on the complexes CpFe(CO)₂(CX)⁺ (X = O, S, Se, and Te) have been used to quantify the nature of bonding between the CX ligands and the metal atom. In addition, conclusions have been reached about the reactivity of the complexes under both nucleophilic and electrophilic attack. The previously established trend of increasing metal—ligand bond strength as X changes from O to S to Se is demonstrated by our molecular orbital calculations, and found to extend to Te. The mechanism for nucleophilic attack, variously explained in the past by either charge control or orbital control, is quantitatively ascribed to orbital control only. The nature of electrophilic attack on these complexes is also found to begin with orbital control.     

Syntheses of Polythioethers Tethered with Bulky Aryl Groups and Their Complexation with Late-Transition Metals

Abstract

New types of o-phenylene-bridged polythioethers tethered with extremely bulky aryl groups at their terminal sulfur atoms, such as TbtS(o-Phen)S(o-Phen)S(o-Phen)STbt (1) and TbtS(o-Phen)S(o-Phen)SS(o-Phen)S(o-Phen)STbt (2) (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, o-Phen = o-phenylene), were synthesized and subjected to the complexation with several kinds of late-transition metals. In the case of polythioether 1, the reaction with RhCl₃·3H₂O in benzene/EtOH resulted in the formation of a unique bimetallic complex, in which a part of ligand 1 is lost and the resulting sulfur atom is directly bound to the other Rh metal center. Interestingly, similar treatment of 1 with IrCl₃·3H₂O afforded ethyl-coordinated mononuclear Ir complex. Furthermore, 1 underwent complexation with Na₂PdCl₄ in EtOH to give the corresponding square planar dichloropalladium complex coordinated with two inner sulfur atoms of 1, while the S₆-ligand 2 reacted with excess of Pd(PPh₃)₄ in benzene to afford a quite interesting trinuclear Pd complex multi-step metal insertion reactions.