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151.
Deprotonated Dithiocarbamic Acid Esters as Thiolate S-Donor Ligands. Structures of Ph(H)NC(S)SMe, Co(PhNC(S)SMe)3, and Cu6(PhNC(S)SMe)6 The reaction of N-phenyl-S-methyldithiocarbamate, PhN(H)C(?S)SMe, ( 1 ) with cobalt(II) and copper(II) salts yields the monomeric compound CoIII(PhNC(S)SMe)3 ( 2 ) and the hexameric compound Cu6I(PhNC(S)SMe)6 ( 3 ). These complexes contain the negatively charged imino-thiolate ligand PhN?C(? S)SMe, which has been formed by deprotonation of 1 . The crystal structures of 1 – 3 have been determined. 1 forms centrosymmetrical dimers through N? H …? S bridge bonds, the conformation in the solid state and in solution is Z,E′. CoIII shows in 2 a trigonal-antiprismatic coordination, with the ligands acting as N,S-chelates. 3 contains an octahedral Cu6-core with Cu …? Cu-distances ranging from 276.3(5) to 305.7(4) pm. Each copper center is trigonally coordinated to one nitrogen and two sulfur atoms of three different ligands. Crystal data: 1 , triclinic, space group P1 , a = 590.5(6), b = 869.0(1), c = 968.5(9) pm, α = 67.29(8), β = 78.44(8), γ = 81.64(9)°, Z = 2, 1 775 reflections, R(Rw) = 0.0317(0.032). 2 , orthorhombic, space group Pbca, a = 978.0(2), b = 1 842.9(4), c = 3 059.7(6) pm, Z = 8, 1 129 reflections, R(Rw) = 0.0997(0.0886). 3 , monoclinic, space group P21/c, a = 1 363.1(3), b = 1 342.8(3), c = 1 671.9(3) pm, β = 103.48°, Z = 2, 1 374 reflections, R(Rw) = 0.0708(0.0617). 相似文献
152.
A. S. Balueva E. I. Ayupova G. N. Nikonov Yu. T. Struchkov A. P. Pisarevskii 《Russian Chemical Bulletin》1994,43(9):1561-1567
Fused 1,3,2-dioxaborinanes, derivatives of 4-diphenylphosphino- and 4-diphenylphosphoryl-4H-1, 3-dioxa-2-boraphenanthrenes, and their complexes with amines have been synthesized. According to X-ray diffraction data, the complex of 2-phenyl-4-diphenylphosphoryl-4H-1, 3-dioxa-2-boraphenanthrene with butylamine exists as a dimer due to the formation of intermolecular hydrogen bonds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1649–1655, September, 1994.The present work was financially supported by the International Science Foundation (grant No. RHBOOO). 相似文献
153.
Structures of New SeII and TeII Complexes Containing 2,2-Dicyanethylene-1,1-dithiolate, 2,2-Dicyanethylene-1,1-thioselenolate, and 2,2-Dicyanethylene-1,1-diselenolate (NBu4)2{Se[S2C?C(CN)2]2} ( I ), (AsPh4)2 · {Te[SSeC?C(CN)2]2} ( II ), and (NBu4)2{Te[Se2C?C(CN)2]2} ( III ) containing the bidentate chelate ligands 2,2-dicyanethylene-1,1-dithiolate i-mnt , 2,2-dicyanethylene-1,1-thioselenolate i-mnts , and 2,2-dicyanethylene-1,1-diselenolate i-mns have been prepared and characterized by X-ray structure analysis. The central units consist of [M(X? X)2E2]2? (M = Se, Te; X? X = ligand; E = lone-pair) with fourfold coordinated SeII and TeII, respectively. The complex anions [Se(i-mnt)2E2]2? as well as [Te(i-mnts)2E2]2? show a trapezoide distortion with d(Se? S) = 2.276(5); 2.287(5); 2.803(5); 2.789(5) Å and d(Te? Se) = 2.611(2); 2.617(3); d(Te? S) = 2.889(5); 2.935(4) Å. In III there are centrosymmetric complex anions [Te(i-mns)2E2]2? with nearly identical Te? Se-bond-lengths: 2.674(3) and 2.692(2) Å. These Te? Se bonds are elongated compared to usual Te? Se bonds. 相似文献
154.
J. Ty Redd Jerald S. Bradshaw Peter Huszthy Reed M. Izatt 《Journal of inclusion phenomena and macrocyclic chemistry》1997,29(3-4):301-308
Pyrimidino-crown ethers were prepared in 30-50% yields by reactingthe ditosylate derivative of the appropriate oligoethylene glycol with4-methoxy-5-methyl-2,6-pyrimidinedimethanol under basic conditions. A newmacrocyclic ligand containing a proton-ionizable pyrimidone subcyclic unitwas prepared in 88% yield by treating the appropriatepyrimidino-crown ether with 5 M NaOH in 50% (v/v) aqueous methanol.Preliminary complexation properties of some of these new compounds werestudied using various NMR spectral techniques. Good enantiomeric recognitionwas exhibited by a chiral pyrimidino-crown ether for the enantiomers of1-(-naphthyl)ethylammonium perchlorate. 相似文献
155.
Some new complexes between thecis-4,4′-dinitrodibenzo-18-crown-6 and rare earth chlorides LnCl3 (Ln=Nd, Gd, Yb) were synthesized in acetonitrile. Ligandcis-4,4′-dinitrodibenzo-18-crown-6 and its complexes were identified by infrared spectroscopy, X-ray diffraction and thermal
analysis (TG and DTA). Acis-trans isomerisation of the complexed ligand is observed about 148°C when heating the rare earth complex.
相似文献
156.
Absorption spectra of the photoexcited (2-C60)Pd(PPh3)2 complex in benzene were obtained by picosecond and nanosecond laser photolysis. The spectra are compared with those observed for photoexcited states of fullerene C60 and charge-transfer states of C60 complexes with ternary amines. The relaxation kinetics of excited (2-C60)Pd(PPh3)2 complex has three components with characteristic lifetimes 1 = 43 ps, 2 = 1500 ps, and 3 = 1.17 s. The results are discussed in terms of the four-level scheme of the excited complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1163–1166, May, 1996. 相似文献
157.
Yannick Ortin Paul O'Donohue Helge Müller-Bunz Anthony R. Manning 《Journal of organometallic chemistry》2004,689(9):1657-1664
Treatment of the aldehyde (η4-C4Ph4)Co(η5-C5H4-CHO) (4b) with tert-butyllithium or phenyllithium yields the secondary alcohols (η4-C4Ph4)Co(η5-C5H4-CH(R)OH), where R=tert-butyl (5) or phenyl (6). Protonation of 5 and 6 at −80 °C furnishes the deep purple, cobalt-stabilized cations, 7 and 8, respectively, both of which exhibit restricted rotation about the external C5H4-CHR+ linkage on the NMR time-scale. These data indicate a minimum value for the barrier to rotation of 15 kcal mol−1, but it is certainly much higher, indicating a considerable degree of C-C double bond character. X-ray crystal structures of 4b, 5 and also of the ketone (η4-C4Ph4)Co(η5-C5H4-C(O)CH3 (4a) are reported. The secondary alcohol 5 exhibits disorder in the solid state because of the presence of diastereomers as a consequence of the stereogenic center at the α-carbon and the clockwise or anticlockwise propeller orientations of the tetraphenylcyclobutadiene ligand. 相似文献
158.
159.
A series of novel bidentate pyrazolone based Schiff base ligands were synthesized by interaction of 4-benzoyl-3-methyl-1-(4′-methylphenyl)-2-pyrazolin-5-one with various aromatic amines like aniline, o-,m-,p-chloroaniline and o-,m-,p-toluidine in a ethanolic medium. All of these ligands have been characterized on the basis of elemental analysis, IR and 1H NMR data. The molecular geometries of five of these ligands have been determined by single crystal X-ray study. Crystallographic study reveals that these ligands exist in the amine-one tautomeric form in the solid state. NMR study also suggests the existence of the amine-one form in solution at room temperature. Ab initio calculations for representative ligand HL1 has been carried out to know the coordination site of the ligand. Novel vanadium Schiff base complexes of these ligands with general formula [OV(L1–7)2(H2O)] have been prepared by interaction of aqueous solution of vanadyl sulfate pentahydrate with DMF solution of the appropriate ligands. The resulting complexes have been characterized on the basis of elemental analysis, vanadium determination, molar conductance and magnetic measurements, thermo gravimetric analysis, infrared and electronic spectral studies. Suitable distorted octahedral structures have been proposed for these complexes. 相似文献
160.
Native non‐covalently bonded protein‐protein and protein‐substrate complexes are of great interest and have been extensively studied by electrospray ionization mass spectrometry (ESI‐MS). Multiply charged protein homomultimeric complexes are shown to form by ESI‐MS. This study addresses factors that can artificially induce the formation of multiply charged protein homomultimeric complexes. Cytochrome c (Cyt c) and ubiquitin, which are monomers in solution, were found to generate (Cyt c)mn+ by electrospray ionization (ESI). The homomultimeric complexes were not limited to dimeric complexes but include also multiply charged trimers, tetramers, and pentamers. The observation of these homomultimeric complexes has never been revealed from a Cyt c solution at the concentration as low as 10 μM. Increasing the concentration of Cyt c enhanced the formation of (Cyt c)mn+ as expected; however, the protein concentration does not affect the relative intensities of monomeric and dimeric complexes. Additionally the enrichment of NH4OH also promotes the formation of (Cyt c)mn+. Notably, source collision‐induced dissociations (source‐CID) of (Cyt c)mn+ alter the charge state distribution (CSD) and may lead to an incorrect interpretation of Cyt c conformations. Hence, extra care should be taken when using CSD to interpret the conformation of a protein derived from ESI‐MS. 相似文献