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1.
The synthesis of lanthanide hydroxo complexes stabilized by a carbon-bridged bis(phenolate) ligand 2,2’-methylene-bis(6-tert-butyl-4-methylphenoxo) (MBMP2−) was described, and their reactivity toward phenyl isocyanate was explored. Reactions of (MBMP)Ln(C5H5)(THF)2 with a molar equiv. of water in THF at −78 °C afforded the bis(phenolate) lanthanide hydroxides as dimers [{(MBMP)Ln(μ-OH)(THF)2}2] [Ln = Nd (1), Yb (2)] in high yields. Complexes 1 and 2 reacted with phenyl isocyanate in THF, after workup, to give the desired O−H addition products, [(MBMP)Ln(μ-η1:η2-O2CNHPh)(THF)2]2 [Ln = Nd (3), Yb (4)] in excellent isolated yields. These complexes were well characterized, and the molecular structures of complexes 2 to 4 were determined by X-ray crystallography. The ytterbium atom in complex 2 is coordinated to six oxygen atoms to form a distorted octahedral geometry, whereas each metal center in complexes 3 and 4 is seven-coordinated, and the coordination geometry can be best described as a distorted pentagonal bipyramid. 相似文献
2.
P.M. Vimal KumarP.K. Radhakrishnan 《Polyhedron》2011,30(17):2849-2855
Five novel nickel(II) complexes have been successfully synthesized with a heterocyclic ligand, Opdac, [Ni(Opdac)2]Cl2 (1), [Ni(Opdac)2(CH3OH)2]Br2(CH3OH)2 (2), [Ni(Opdac)2]I2 (3), [Ni(Opdac)2NO3]NO3 (4) and [Ni(Opdac)2ClO4]ClO4 (5) where Opdac = 4-(1-H-1,3-benzimidazole-2-yl)-1,5-dimethyl-2-phenyl-1-2-dihydro-3-H-pyrazol-3-one. All the complexes were characterized by elemental analysis, molar conductivity, CHN analysis, magnetic susceptibility measurements, spectroscopic studies and TG/DTA methods. In all the complexes, Opdac acts as a bidentate ligand coordinating to Ni(II) ion via the benzimidazole imine nitrogen and the pyrazolone oxygen atoms. The complexes 1 and 3 have a tetrahedral geometry while 2, 4 and 5 have an octahedral geometry around the Ni(II) center. 相似文献
3.
Homoleptic Ce(III) and Nd(III) triamides [LnL(3)] [Ln = Ce(1) or Nd(2)] and the heterobimetallic amide-alkoxide derivatives [LnL(2)(mu-OBu(t))2M(tmeda)] [Ln = Ce, M = Na (3); Ln = Nd, M = Na (4); Ln = Nd, M = K (5)] supported by the bulky [N(SiBu(t)Me2)(2-C(5)H(3)N-6-Me)]- ligand (L-) have been successfully synthesized and characterized. Complexes 1-3 and 5 show a high activity toward the ring-opening polymerization of epsilon-caprolactone. 相似文献
4.
The reaction between 3-hydroxy-5-hydroxymethyl-2-methyl-4-pyridinecarboxaldehyde semicarbazone (pyridoxal-semicarbazone or PLSC) and appropriate chloride, sulfate, nitrate or thiocyanate Cu(II) salts in water/alcohol mixtures resulted in the formation of new copper(II) complexes: [Cu(PLSC)Cl2] (1), [Cu(PLSC)(H2O)(SO4)]2·3H2O (2), [Cu2(PLSC)2(NCS)2](NCS)2 (3), [Cu(PLSC)(NO3)2(CH3OH)] (4) and [Cu(PLSC-2H]NH3·H2O (5). The complexes were characterized by elemental analysis, conductometric measurements and IR spectroscopy, while complexes 1, 2, 3 and 4 were further characterized by single crystal X-ray diffraction. 相似文献
5.
《Polyhedron》2002,21(9-10):1043-1050
A new chiral P,N-donor iminophosphine ligand was used to synthesize a series of palladium(II) and platinum(II) complexes. Single crystal X-ray analysis showed that in all cases the P,N ligand forms a six-membered chelate ring, and the square-planar coordination of the metal atom is completed by two halide ions, two methyl groups, or one methyl group and one halide ion. In the latter instance, the methyl group is cis to the phosphorus atom. 相似文献
6.
Four new solvent-induced Cu(II) complexes with the chemical formulae [{Cu(HL)(CH3OH)}2Cu] · CH3OH (1), [{(Cu(HL))2(CH3CH2OH)2}Cu] (2), [{CuL(H2O)}2Cu2] · 2CH3CH2CH2OH (3) and [{(Cu(HL))2(CH3CH2CH2CH2OH)2}Cu] (4), where H4L = 6,6′-dihydroxy-2,2′-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol, have been synthesized and characterized by elemental analyses, 1H NMR, FT-IR, UV–Vis spectra, TG-DTA, molar conductances and X-ray crystallography. Complexes 1, 2 and 4 have an elongated square-pyramidal geometry with an unusually long bond from the penta-coordinated Cu(II) centres to the oxygen atoms of the apically coordinated solvent (methanol, ethanol or n-butanol) molecules for the terminal Cu(II) ions, and a square planar geometry distorted tetrahedrally for the central Cu(II) ion. In complex 3, the terminal Cu(II) ions have trigonal bipyramidal coordination geometries constituted by equatorial O2N donor sites, with one oxygen atom from one of the coordinated water molecules and one nitrogen atom from a completely deprotonated L4− ligand unit in the axial positions, and the central Cu(II) ions are in slightly tetrahedrally distorted square planar geometries constituted by four phenoxo oxygen donors from two completely deprotonated L4− ligand units, and these form a tetrametal Cu–O–Cu–O–Cu–O–Cu–O eight-membered ring. These four complexes exhibit strong hydrogen bonding interactions in the solid state. Moreover, co-crystallizing n-propanol molecules link two other adjacent complex molecules into a self-assembled infinite 2D supramolecular structure via the intermolecular hydrogen bonds in complex 3. 相似文献
7.
8.
Takashi Tsuno Yu Sugiyama Henri Brunner Michael Bodensteiner Kosei Lee 《Journal of Coordination Chemistry》2017,70(20):3459-3470
Treatment of NiCl2 with the tripod ligand (LMent,SC)-1H led to (LMent,SC)-[Cp(PNMent)NiCl] in which the potentially tridentate ligand coordinated to the metal center in a bidentate way via the cyclopentadienyl system and the phosphorus atom. In the presence of NH4PF6 [(LMent,SC)-[Cp(PNMent)NiCl] readily underwent Cl/PPh3 exchange to give (LMent,SC)-[Cp(PNMent)NiPPh3]PF6. Reaction of (LMent,SC)-[Cp(PNMent)NiCl] with 0.5 eq. of dppe afforded [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2. (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 and [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 were characterized by NMR and MS spectroscopy, and also by single crystal X-ray diffraction. The cyclopentadienyl ligand of (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 shows a distortion intermediate between the ene-allyl and diene types, while the two cyclopentadienyl ligands of [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 have intermediate and diene distortions, respectively. According to the temperature dependent NMR spectra of (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 and [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 two different conformations of the tether in the Cp(PNMent)Ni system could be frozen out at low temperatures. 相似文献
9.
A series of nonanuclear lanthanide oxo-hydroxo complexes of the general formula [Ln(9)(mu(4)-O)(2)(mu(3)-OH)(8)(mu-BA)(8)(BA)(8)](-)[HN(CH(2)CH(3))(3)](+).(CH(3)OH)(2)(CHCl(3)) (BA = benzoylacetone; Ln = Sm, 1; Eu, 2; Gd, 3; Dy, 4; Er, 5) were prepared by the reaction of hydrous lanthanide trichlorides with benzoylacetone in the presence of triethylamine in methanol and recrystallized from chloroform/methanol (1:10) at room temperature. These five compounds are isomorphous. Crystal data for 1: cubic, Pn3n; T = 180 K; a = 33.8652(4) A; V = 38838.4(8) A(3); Z = 6; D(calcd) = 1.125 g cm(-)(3); R1 = 3.37%. Crystal data for 2: cubic, Pn3n; T = 180 K; a = 33.8252(8) A; V = 38700.9(16) A(3); Z = 6; D(calcd) = 1.133 g cm(-)(3); R1 = 4.97%. Crystal data for 3: cubic, Pn3n; T = 180 K; a = 33.7061(6) A; V = 38293.5(12) A(3); Z = 6; D(calcd) = 1.157 g cm(-)(3); R1 = 5.13%. Crystal data for 4: cubic, Pn3n; T = 180 K; a = 33.5900(7) A; V = 37899.2(14) A(3); Z = 6; D(calcd) = 1.182 g cm(-)(3); R1 = 4.03%. Crystal data for 5: cubic, Pn3n; T = 180 K; a = 33.5054(8) A; V = 37613.6(16) A(3); Z = 6; D(calcd) = 1.202 g cm(-)(3); R1 = 4.86%. The core of the anionic cluster comprises two vertex-sharing square-pyramidal [Ln(5)(mu(4)-O)(mu(3)-OH)(4)](9+) units. The compounds were characterized by elemental analysis, IR, fast atom bombardment mass spectra, thermogravimetry, and differential scanning calorimetry. The thermal analysis indicated that the nonanuclear species were stable up to 150 degrees C. Luminescence spectra of 2 and magnetic properties of 1-5 were also studied. 相似文献
10.
The [(PPh3)2RuHCl(CO)(Hmtpo)] complex has been prepared and studied by IR, NMR, UV–VIS spectroscopy and X-ray crystallography. The complex was prepared in reactions of [RuHCl(CO)(PPh3)3] with 7-hydroxy-5-methyl[1,2,4]triazolo[1,5-a]pyrimidine in methanol. The electronic structure and UV–Vis spectrum of the obtained compound have been calculated using the TD–DFT method. 相似文献
11.
Several of alkaline-earth-metal complexes [(η(2):η(2):μ(N):μ(N)-Li)(+)](2)[{η(2)-Me(2)Si(DippN)(2)}(2)Mg](2-) (4), [η(2)(N,N)-Me(2)Si(DippN)(2)Ca·3THF] (5), [η(2)(N,N)-Me(2)Si(DippN)(2)Sr·THF] (6), and [η(2)(N,N)-Me(2)Si(DippN)(2)Ba·4THF] (7) of a bulky bis(amido)silane ligand were readily prepared by the metathesis reaction of alkali-metal bis(amido)silane [Me(2)Si(DippNLi)(2)] (Dipp = 2,6-i-Pr(2)C(6)H(3)) and alkaline-earth-metal halides MX(2) (M = Mg, X = Br; M = Ca, Sr, Ba, X = I). Alternatively, compounds 5-7 were synthesized either by transamination of M[N(SiMe(3))(2)](2)·2THF (M = Ca, Sr, Ba) and [Me(2)Si(DippNH)(2)] or by transmetalation of Sn[N(SiMe(3))(2)](2), [Me(2)Si(DippNH)(2)], and metallic calcium, strontium, and barium in situ. The metathesis reaction of dilithium bis(amido)silane [Me(2)Si(DippNLi)(2)] and magnesium bromide in the presence of oxygen afforded, however, an unusual lithium oxo polyhedral complex {[(DippN(Me(2)Si)(2))(μ-O)(Me(2)Si)](2)(μ-Br)(2)[(μ(3)-Li)·THF](4)(μ(4)-O)(4)(μ(3)-Li)(2)} (8) with a square-basket-shaped core Li(6)Br(2)O(4) bearing a bis(aminolato)silane ligand. All complexes were characterized using (1)H, (13)C, and (7)Li NMR and IR spectroscopy, in addition to X-ray crystallography. 相似文献
12.
A novel neutral mixed-valent Cu(I)Cu(II)(2) triangular metallomacrocycle [Cu(3)L(2)(HL)].3CH(3)OH.2H(2)O (1) was assembled by reaction of the tetradentate ligand bis(N-salicylidene-4,4'-diphenylamine), H(2)L, with a copper(II) salt. ESI-MS show peaks only corresponding to the triangular structural species, indicating the high stability of the trimer structure in solution. Magnetic study confirms that there are two Cu(II) ions and one Cu(I) ion in a discrete triangular molecule. The crystal structure of 1 reveals that the triangle is formed by three deprotonated ligands and three copper ions with a Cu-Cu separation of ca. 11.8 A. Each copper atom is coordinated by two oxygen atoms and two nitrogen atoms from two different bis-bidentate ligands in a heavily distorted tetrahedral geometry, while each ligand is bound to two metal ions in a bis-bidentate coordination mode and links the metal centers overlapping in an unprogressive manner. Strong intramolecular pi.pi interactions between the ligands are found to stabilize the constraint conformation of the triangle. Electrochemical study reveals that the mixed-valent Cu(I)Cu(II)(2) complex is the most stable state in solution condition, and the electrochemical communication between the copper ions might be explained on the basis of the through-bond interaction. UV-vis-NIR spectral measurement demonstrates the Robin-Day class II behavior of the mixed-valence compound with a weak copper-copper interaction. 相似文献
13.
The binuclear cobalt(II) amide complex [(CoL2)2-(TMEDA)] (1) [L = N(Si(t)BuMe2)(2-C5H3N-6-Me); TMEDA = Me2NCH2CH2NMe2] has been synthesized by the reaction of anhydrous CoCl2 with 2 equiv of [Li(L)(TMEDA)]. X-ray crystallography revealed that complex 1 consists of two [CoL2] units linked by one TMEDA ligand molecule, which binds in an unusual N,N'-bridging mode. Protolysis of 1 with the bulky phenol Ar(Me)OH (Ar(Me) = 2,6-(t)Bu2-4-MeC6H2) and thiophenol ArSH (Ar = 2,4,6-(t)Bu3C6H2) gives the neutral monomeric cobalt(II) bis(aryloxide) [Co(OAr(Me))2(TMEDA)] (2) and dithiolate [Co(SAr)2(TMEDA)] (3), respectively. Complexes 1-3 have been characterized by mass spectrometry, microanalysis, magnetic moment, and melting-point measurements, in addition to X-ray crystallography. 相似文献
14.
15.
Vimal K. Jain 《Transition Metal Chemistry》1996,21(6):494-497
Summary Binuclear PdII and PtII complexes of the type [M2Cl2(-Opy)2(PR3)2] [M = Pd or Pt; Opy = 2-OC5H4N (2-hydroxypyridinate ion); PR3 = PEt3, Pn-Bu3, PMe2Ph or PMePh2] were synthesized and characterized by elemental analysis, 1H- and 31P-n.m.r. spectroscopies. The Pd complexes exist in the sym trans form, whereas the corresponding Pt complexes were generated as different isomers. 相似文献
16.
İlyas Gönül Ender Fakı Burak Ay Muhammet Köse Selahattin Serin 《Transition Metal Chemistry》2018,43(1):73-81
A Schiff base ligand (HL), 2,4-dimethoxy-N-(5-chloro-2-hydroxybenzylidene)-benzenamine, derived from 5-chloro-2-hydroxybenzaldehyde and 2,4-dimethoxyaniline, and its metal complexes [Co(L)2]·CH3OH (1), [Ni(L)2] (2), [Cu(L)2] (3) have been synthesized. The compounds were characterized by analytical and spectroscopic methods. In addition, the structures of the Schiff base HL and its Co(II) complex were determined by single-crystal X-ray analysis. The Co(II) center is six-coordinate, being coordinated to two imine nitrogen, two phenolate oxygen and two methoxy oxygen atoms of two crystallographically independent Schiff base ligands. Luminescence properties of HL and its complexes were investigated both in solution and in the solid state. 相似文献
17.
The reactions of prop-2-ynyltriphenylphosphonium bromide with a series of primary aromatic or aliphatic amines in refluxing acetonitrile generated the corresponding 2-hydrocarbylaminoprop-1-enyltriphenylphosphonium bromide [RNHC(Me)=CHPPh(3)]+Br- (R = 2,6-C(6)H(3)iPr(2) (1a), 2,6-C(6)H(3)Me(2) (1b), Ph (1c), t-Bu (1d)) as crystalline solids. Deprotonation of 1a-d with NaH in THF at -35 degrees C afforded the alpha-iminophosphorus ylides RN=C(Me)CH=PPh(3) (2a-d) in high yield. Spectroscopic and crystallographic data of 2 suggest a strong intramolecular interaction between the imino nitrogen and the phosphorus atom. In contrast to N-arylated 2a-c, the N-tert-butyl-derived 2d is extremely moisture-sensitive. Hydrolysis of 2d led to elimination of benzene and generated concomitantly the phosphine oxide 3d that contains an ene-amine functionality. The reactions of 2a-c with Ni(COD)(2) in the presence of an excess amount of pyridine in toluene produced the divalent nickel complexes of the type [kappa(2)-RNC(Me)=CHPPh(2)]Ni(Ph)(Py) (4a-c). The solution and solid-state structures of these new compounds are presented. 相似文献
18.
A novel macrocyclic tetradentate ligand 1,5,8,12-tetraaza-2,4,9,11-tetraphenyl-6,7:13,14-dibenzocyclohexadeca- 1,4,8,11-tetraene
(L) has been synthesized. Cobalt(II), nickel(II), and copper(II) complexes of this ligand have been prepared and characterized
by elemental analysis, molar conductance measurements, magnetic susceptibitity measurements, and mass, IR, electronic, and
ESR spectral studies. The molar conductance measurements correspond to a nonelectrolytic nature for all the complexes, which
can be formulated as [M(L)X2] (where M = Co(II), Ni(II), and Cu(II); X = Cl− and NO3−). On the basis of IR, electronic, and ESR spectral studies, an octahedral geometry has been assigned to the Co(II) and Ni(II)
complexes, whereas a tetragonal geometry was found for the Cu(II) complexes. The investigated compounds and uncomplexed metal
salts and the ligands were tested against bacterial species like Sarcina lutea, Escherchia coli, and Staphylococcus aureus. The metal complexes have higher activity than the free ligand and metal salts.
The text was submitted by the authors in English. 相似文献
19.
A novel terpyridine ligand containing a pentaphenylphenyl moiety linked to the terpyridyl core (1-terpyridyl-2,3,4,5,6-pentaphenyl-benzene (TPPPB)) has been synthesized in good yield and reacted with Pt(DMSO)2Cl2, to produce the cationic complex [Pt(TPPPB)Cl]Cl (5). 5 was studied structurally and spectroscopically. It is observed to be brightly luminescent in the solid state at room temperature and at 77 K, with no change in lambdaem(max). The complex exhibits reversible vapochromic behavior upon exposure to methylene chloride vapors, changing color from red (5-R) to green (5-G). The shift to higher energy in the emission maximum from 654 to 514 nm is the largest vapochromic shift (140 nm) yet reported. The [Pt(TPPPB)Cl]Cl complex exhibits high selectivity for certain volatile organic compounds (VOCs) including methylene chloride, ethanol, ethyl acetate, and acetonitrile. The crystal structures of both the green and red forms have been determined by single-crystal X-ray diffraction. In both forms, the cationic Pt(II) complex possesses the anticipated square-planar coordination geometry that is distorted as a consequence of constraints from the terpyridyl binding. Analysis of the crystal packing of the green form (5-G) reveals the presence of non-interacting Pt...Pt separations with distances of 3.9092(9) and 4.5483(11) A and a zigzag arrangement between neighboring Pt(II) ions. The red form (5-R) contains complexes that are stacked with Pt...Pt separations of 3.2981(14) and 3.3427(14) A, indicative of metallophilic interaction. The change in the emitting state, as a consequence of the effect of the volatile organic compounds, results from a disruption of the d8-d8 metallophilic interactions in the red form and its metal-metal-to-ligand charge transfer (MMLCT) excited state to a more-localized Pt(dpi)-to-tpy(pi*) metal-to-ligand charge transfer (MLCT) excited state in the green form. 相似文献
20.
Meiners J Scheibel MG Lemée-Cailleau MH Mason SA Boeddinghaus MB Fässler TF Herdtweck E Khusniyarov MM Schneider S 《Angewandte Chemie (International ed. in English)》2011,50(35):8184-8187
Squaring the circle: the novel dienamido pincer ligand N(CHCHPtBu(2))(2)(-) affords the isolation of the unusual square-planar iridium(II) and iridium(III) amido complexes [IrCl{N(CHCHPtBu(2))(2)}](n) (n=0 (1), +1 (2)). In contrast, the corresponding iridium(I) complex of the redox series (n=-1) is surprisingly unstable. The diamagnetism of 2 is attributed to strong N→Ir π donation. 相似文献