Insertion of sulphur dioxide into nickelcarbon σ bonds. X-ray structure of [bis(2-diphenylphosphinoethyl)phenylphosphinenickel-o-methylsulfinato] tetraphenylborate

Sulphur dioxide reacts with [NiCH₃(ppp)]BPh₄ (ppp = bis(2-diphenylphosphinoethyl)phenylphosphine) to give the O-methylsulfinate complex [NiOS(O)CH₃(ppp)]BPh₄. The crystal structure of the compound has been determined by X-ray diffraction analysis.     

双[2-(2'-苯氧基)苯并恶唑]二吡啶合锰(II)配合物的研究

X射线晶体结构分析结果表明, 标题化合物晶体(C36H26MnN4O4)属单斜晶系, 空间群为P21/a, a=0.9833(3), b=1.8646(3),c=0.9449(1)nm, Z=2, 最终因子Rw=0.057。利用热重分析对配合物晶体两步热分解过程进行了非等温热力学研究, 探讨了反应的可能机理, 得到其相应的动力学参数。第一步非等温动力学方程为: dα/dt=A.exp(-E/RT).2(1-α)^1^/^2, 第二步: dα/dt=A.exp(-E/RT).3/2(1-α)[-ln(1-α)]^1^/^3。     

The Synthesis and Structure of Hexakis(dimethylphenylphosphonite)ruthenium(II) bis[tetraphenylborate(–1)]

Abstract . Treatment of the hydrazine salt [Ru(COD)(H₂NNH₂)₄][BPh₄]₂ with excess of P(OMe)₂Ph in acetone gave a homoleptic complex trans‐[Ru{P(OMe)₂Ph}₆][BPh₄]₂, which was characterized by IR, ³¹P{¹H}, ¹³C{¹H}, and ¹H NMR spectroscopy, elemental analysis, and X‐ray crystallography. The ruthenium in the complex has distorted octahedral coordination arrangement and bonded to all the six P(OMe)₂Ph molecules through the phosphorus atoms.     

Synthesis and x-ray crystal structure of tetraethylammonium bis[1, 1-dicyanoethylene-2, 2-dithiolato]platinate(II)

Summary [(NEt₄)]₂[Pt(S₂C₄N₂)₂] has been prepared from K₂PtCl₄ and K₂S₂C₄N₂·H₂O with NEt₄Cl and characterized by single crystal x-ray structural analysis.The title compound crystallizes in the monoclinic space group P2₁/a witha=14.800(2),b=11.679(2),c=9.497(1) Å, =94.51(4)° andZ=2. In the complex anion Pt sits on a centre of symmetry and is coordinated by four S atoms of the ligand (S₂C₄N₂)^2– (i-mnt). The Pt–S distances are 2.315(3) and 2.316(3) Å. The intra-and interligand S–S distances are 2.807(4) and 3.682(4) Å, respectively, indicating the rectangular planar arrangement of the sulfurs about platinum. Within the isomaleonitriledithiolate there is still some suggestion of resonance indicated by the geometry of i-mnt.     

Synthesis and X-ray crystal structure of [2-(phosphinomethyl)ferrocenyl]diphenylphosphine

[2-(Phosphinomethyl)ferrocenyl]diphenylphosphine 2, is an air stable primary phosphine bearing a 1,2-disubstituted ferrocene framework, which has been prepared by reduction of the corresponding phosphonate. Confirmation of its structure has been obtained by X-ray single-crystals diffraction analysis. Despite its high stability toward oxidation, phosphine 2 still displays a normal coordinative behaviour toward [(p-cymene)RuCl₂]₂. The expected (p-cymene)RuCl₂(phosphine) complex is formed by coordination of the primary phosphine function, while the conceivably competitive complexation of the PPh₂ group was not observed.     

Synthesis and X-ray crystal structure of tetraethylammonium bis[1,2-di(carbomethoxy)ethane-1,2-dithiolato]oxotechnetate(V)

Summary The (NEt₄)⁺[TcO{SCH(CO₂Me)CH(CO₂Me)}₂]^– compound has been prepared from technetium(V) gluconate and characterized by single crystal x-ray structural analysis (R factor=0.065).The compound crystallizes in the monoclinic space groupP2₁/c witha=12.722(3),b=13.820(4) andc=18.213(5) Å, =107.13(4)° andZ=4. In the complex the technetium atom is close to the center of the base of a square pyramid in which the oxo oxygen is at the apex and the four sulfur atoms form the basal plane. The Tc-S distances average 2.316 Å. The Tc=O distance is 1.672(6) Å. Considerations about the osteotropic behaviour of DMSA labelled with⁹⁹Tc are deduced from the reported results.     

Synthesis of novel bis(chromenes) and bis(chromeno[3,4-C]pyridine) incorporating piperazine moiety

Novel bis(2-oxo-2H-chromene) as well as bis(2-imino-2H-chromene) derivatives incorporating piperazine moiety were prepared by the cyclocondensation reaction of bis(2-hydroxybenzaldehyde) with two equivalents of each of the appropriate β-ketoesters or acetonitrile derivatives. The bis(2-imino-2H-chromene-3-carbothioamide) derivative was used as a key synthon for construction of novel bis(3-(4-substituted thiazol-2-yl)-2H-chromen-2-one) derivatives via its cyclocondensation with a series of the appropriate α-halocarbonyl derivatives. Moreover, the bis(2-hydroxybenzaldehyde) reacted with four equivalents of the appropriate acetonitrile derivatives to afford the corresponding bis(3H-chromeno[3,4-c]pyridine) derivatives. Elucidation of the structure of the novel bis(chromenes) bearing piperazine nucleus was established by the spectral data and elemental analyses.     

Synthesis and structure of novel [Ph(RO)PSe2]- complexes

Reaction of (PhPSe2)2(Woollins reagent) with NaOR (R = Me, Et, (i)Pr) gives the non-symmetric phosphonodiselenoato anions [Ph(RO)PSe2]- which can be complexed to a range of metals. The nickel complex Ni[Ph(MeO)PSe2]2 adopts a square-planar ML2 structure while the cadmium complex Cd[Ph(MeO)PSe2]2 displays a dimeric M2L4 structure. Two different lead complexes are observed, one consisting of PbL2 units joined by Pb...Se interactions to form distinct dimeric pairs. The other displays a novel dimeric structure built around a central four-membered Pb2Se2 ring. All new compounds have been characterised spectroscopically (31P, 1H, 13C NMR, IR, mass spectroscopy), by elemental analysis and five demonstrative X-ray structures are reported.     

Synthesis and liquid-crystalline properties of copper(II) bis[4-heptyloxy-N-(aryl)benzaldimine-2-olates]

We describe the synthesis and liquid-crystalline properties of copper complexes with Schiffs bases. We show that when going from ligands to complexes, the mesophase interval narrows until it disappears and the phase transition temperature increases. In contrast to the case for ligands, no linear relationship is observed between the thermal stability of complexes and the electronic properties. The variation in the clearing point in the series of complexes with alkyl substituents is consistent with the even-odd contributions of the polarizability of the radicals to the total polarizability of the compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2833–2838, December, 1989.     

Synthesis and crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis[dichloro(thiocyanato)copper(II)]

A new complex salt [4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane bis[dichloro(thiocyanato)copper(II)], [H₂(Crypt-222)][CuCl₂(SCN)]₂, is synthesized and studied by X-ray diffraction analysis. The crystals are monoclinic (space group C2/c, a = 14.603 Å, b = 8.330 Å, c = 25.091 Å, β = 100.76°, Z = 4). The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.047 for 2943 independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). The Cu²⁺ cations and Cl^? and SCN^? anions form infinite polymeric chains of spiro-conjugated alternating centrosymmetric four-membered CuCl₂Cu cycles and eight-membered Cu(SCN)₂Cu cycles through coordination bonds. The coordination polyhedron of the Cu²⁺ cation is a distorted trigonal bipyramid. The [H₂(Crypt-222)]²⁺ dication contains trifurcate N⁺-(…O)₃ bonds on axis 2.     

Synthesis and structural characterization of cadmium(II) complexes of tetramethylthiourea (Tmtu); X-ray structure of [Cd(Tmtu)2Cl2]

The spectral characterization of cadmium(II) complexes of the general formula [Cd(Tmtu)₂X₂] (Tmtu = tetramethylthiourea, X = Cl^?, Br^?, I^?, and SCN^?) as well as the X-ray structure of one of them, [Cd(Tmtu)₂Cl₂] (I) is described. In (I), the cadmium atom lies on a twofold rotation axis and has a distorted tetrahedral coordination environment defined by two S atoms of telramelhylthioures (Tmtu) ligands and two chloride ions. The crystal structure is stabilized by non-classical intramolecular C-H?N and C-H?S hydrogen bonding interactions involving the methyl H and sulfur or nitrogen atoms. The spectroscopic data were discussed in terms of the nature of bonding.