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1.
《Journal of Coordination Chemistry》2012,65(5):747-765
Continued exploration of the coordination behavior of derivatives of 2-benzophenone-based ligands with metal alkoxides ([M(OR)4]) was undertaken from the reaction of 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid (H2-OBzA) with a series of Group 4 precursors. The products of these reactions were identified as: [(OR)2Ti(μ-(c,c-OBzA))]2 (OR?=?OCHMe2 (OPri; 1 ?2tol); OCMe3 (OBut; 2 ?THF); OCH2CMe3 (ONep; 3)), [[(OPri)3Ti(μ-OPri)Ti(OPri)2]2(μ-(μc,μ-OBzA))2]2 (4), [(ONep)3Zr(μ-ONep)2Zr(ONep)2]2(μ-(c,μ-OBzA)2) (5 ?tol), [(py)(OBut)3Zr]2(μ-(c,c-OBzA)) (6), [(OBut)2Hf(μ-OBut)]2(μ-(c,η1-OBzA)) (7) where ‘c’?=?chelating or η2; ‘μ’?=?bridging or η1,η1(O,O’); and μc?=?bridging chelating or η1,η1(O,O’); η2?:?η1. The metal centers for each of these compounds adopt a pseudo-octahedral geometry employing the OBzA ligand in numerous binding modes. The different functional oxygens (carboxylate, hydroxyl, and carbonyl) were employed in a variety of coordination modes for 1–7. The complexity of these OBzA-modified compounds is driven by a combination of the coordination behavior of the OBzA moieties, the size of the metal cation, and the pendant chain of the OR ligand. Solution NMR indicates a complex structure exists in solution that was considered to be consistent with the solid-state structure. 相似文献
2.
《Journal of Coordination Chemistry》2012,65(3):487-505
Investigation of the coordination behavior of 4,4′-methylenebis(2,6-di-tert-butylphenol) (or H2-4DBP) with a series of metal alkoxides led to isolation of [(OR)3M]2(µ-4DBP), where M/OR?=?Ti/OBut (2), Ti/ONep (3), Zr/OBut (4), Hf/OBut (5), and [(py)(OR)3M]2(µ-4DBP)?·?py (5a), where py?=?pyridine and ONep?=?OCH2C(CH3)3. Metal alkyl derivatives of 4DBP were also studied and found to form similar di-substituted species: [(py)2(Et)Zn]2(µ-4DBP)?·?py (6), [(THF)3(Br)Mg]2(µ-4DBP) (7), [(THF)2(Br)Mg](µ-4DBP)[Mg(Br)(THF)3]?·?(THF, tol) (7a), and [(py)(R)2Al]2(µ-4DBP), where R?=?CH3 (8), Et (9), CH2CH(CH3)2 (10); tol?=?toluene and THF?=?tetrahydrofuran. All structures demonstrate the bridging nature of 4DBP and the ability to bind a variety of metal centers. Solution state NMR indicates that the structures of 2–10 are retained in solution. Thermal analyses indicate that 4DBP is preferentially lost during heating. 相似文献
3.
Treatment of [Ru(PPh3)3Cl2] with one equivalent of tridentate Schiff base 2-[(2-dimethylamino-ethylimino)-methyl]-phenol (HL) in the presence of triethylamine afforded a ruthenium(III) complex [RuCl3(κ2-N,N-NH2CH2CH2NMe2)(PPh3)] as a result of decomposition of HL. Interaction of HL and one equivalent of [RuHCl(CO)(PPh3)3], [Ru(CO)2Cl2] or [Ru(tht)4Cl2] (tht = tetrahydrothiophene) under different conditions led to isolation of the corresponding ruthenium(II) complexes [RuCl(κ3-N,N,O-L)(CO)(PPh3)] (2), [RuCl(κ3-N,N,O-L)(CO)2] (3), and a ruthenium(III) complex [RuCl2(κ3-N,N,O-L)(tht)] (4), respectively. Molecular structures of 1·CH2Cl2, 2·CH2Cl2, 3 and 4 have been determined by single-crystal X-ray diffraction. 相似文献
4.
Mono- and bi-nuclear Zr(IV) β-ketodiester complexes of general formulas [Zr(dtbacdc)4] (1), [Zr(dmacdc)3(OiPr)]2 (2), and [Zr(dtbacdc)3(OiPr)]2 (3), (dtbacdc = di-tert-butyl-1,3-acetonedicarboxylato and dmacdc = dimethyl-1,3-acetonedicarboxylato ligands) were successfully isolated, when zirconium(IV)
isopropoxide reacted with the four- ((1)) or twofold ((2), (3)) excess of di-alkyl 1,3-acetonedicarboxylates (CO(CH2COOR′)2, R′ = Me, tBu). Analysis of single-crystal X-ray diffraction data showed that (1) crystallizes in the monoclinic system (C 2/c (no. 15)). The structure of this compound consists of monomers, which are composed of Zr(IV) ions surrounded by eight oxygen
atoms derived from four chelating β-ketodiester ligands. The stoichiometry and the bi-nuclear structure of (2) and (3) using spectroscopic methods (IR and NMR), and mass spectrometry have been determined. Thermal analysis and variable temperature
IR (VT-IR) spectroscopy have been used to study the thermal stability and thermal decomposition pathway of synthesized Zr(IV)
compounds. 相似文献
5.
Michael Veith Charu Mathur Volker Hugh 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):489-492
The synthesis of the new heteroleptic heterotrimetallic cluster, [(C5H5)Sn(μ-OBut)2Ge(OBut)Mo(CO)5] (1) has been achieved by a thermally induced CO substitution of the transition metal derivative, Mo(CO)6, by the basic germanium atom of the cyclopentadienyl heterobimetallic alkoxide, [(C5H5)Sn(μ-OBut)2Ge(OBut)]. The microanalysis, molecular weight (monomer in benzene), IR and multinuclear NMR data and X-ray diffraction study is consistent with the formulation of 1. The Sn atom has a trigonal pyramidal coordination environment formed by a aysmmterically π-bonded terminal C5H5 ring and two symmetrically bridged tert-butoxy groups. The four-coordinate Ge atom lies at the centre of a distorted tetrahedron and is terminally attached to a tert-butoxy group and a Mo(CO)55? fragment. 相似文献
6.
tBuN = VCl2 · 1,2-Dimethoxoethane, a Precursor in the Synthesis of Binuclear Diamagnetic tert -Butylimidovanadium(IV) Compounds Syntheses of the paramagnetic tert-butylimidovanadium(IV) complexes tBuN = VCl2 · DME ( 7 ), tBuN = VCl2 · 2 L (L = 1,4-dioxane, thf, PMe3, PEt3, pyridine) and tBuN = VBr2 · DME are described; the free Lewis acids has been found by mass spectroscopy to be the binuclear compounds [(μ-NtBu)2V2Cl4] und [(μ-NtBu)2V2Br4]. 7 reacts with LiOR, LiOAr and LiNR2 forming binuclear diamagnetic tert-butylimidovanadium(IV) compounds: [(μ-NtBu)2V2Cl2(OiPr)2] ( 18 ), [(μ-NtBu)2V2(OR)4], [(μ-NtBu)2V2Cl2(OAr)2], [(μ-NtBu)2V2(OAr)4] and [(μ-NtBu)2V2Cl2(NR2)2]. In additional experiments the complexes [(μ-NtBu)2V2(CH2CMe3)2(OAr)2], [(μ-NtBu)2V2Me2(NR2)2], [(μ-NtBu)2V2Cl4] and tBuN = V(OAr)3 has been prepared. All compounds obtained are characterized by spectroscopic methods (MS; 1H, 13C, 51V NMR), [(μ-NtBu)2V2Cl2(NtBuSiMe3)2] ( 21 ) by single crystal x-ray diffraction. For 18 the presence of cis/trans isomeres was shown by NMR spectroscopy. The 51V NMR spectra of the binuclear diamagnetic vanadium (IV) compounds are discussed. 相似文献
7.
《Journal of Coordination Chemistry》2012,65(18):3265-3272
Three new centrosymmetric dinuclear copper(II) complexes, [Cu2Cl2(L1)2] (1), [Cu2(μ 1,3-NCS)2(L2)2] (2), and [Cu2(μ 1,1-N3)2(L3)2] (3), where L1, L2, and L3 are the deprotonated forms of the Schiff bases 1-[(2-propylaminoethylimino)methyl]naphthalen-2-ol (HL1), 1-[(3-methylaminopropylimino)methyl]naphthalen-2-ol (HL2), and 2-[(2-isopropylaminoethylimino)methyl]phenol (HL3), respectively, have been prepared and characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Each Cu is coordinated by the three donors of the Schiff bases and by two bridging groups, forming a square-pyramidal geometry. 相似文献
8.
9.
《Journal of Coordination Chemistry》2012,65(10):1664-1675
Three coordination polymers, {[Co(C10H5N3O5)(H2O)2]·H2O}n (1), {[Mn3(C10H5N3O5)2Cl2(H2O)6]·2H2O}n (2), and {[Cu3(C10H4N3O5)2(H2O)3]·4H2O}n (3), based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide (H3DCImPyO), were synthesized under hydrothermal conditions. The polymers showed diverse coordination modes, being characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray structure analysis. In 1, the HDCImPyO2? generated a 1-D chain by adopting a μ2-kN, O : kN′, O′ coordination mode to bridge two Co(II) ions in two bis-N,O-chelating modes. In 2, the HDCImPyO2? adopted a μ3-kN, O : kO′, O′′ : O′′′ coordination mode to bridge two crystallographically independent Mn(II) ions, forming a 2-D hcb network with {63} topology. In 3, by adopting μ4-kN, O : kO′, O′′ : kN′′, O′′′ : O′′′′ coordination, DCImPyO3? bridged three crystallographically independent Cu(II) ions to form a 3-D framework having the stb topology. 相似文献
10.
《Journal of Coordination Chemistry》2012,65(7):1167-1176
In thermal reactions of the doubly bridged dicyclopentadienes (C5H3R(SiMe2))(C5H3R(GeMe2)) (R=H (1), tBu (5)) with Mo(CO)6, the bridging GeMe2 is cleaved to give the corresponding degermylated products [(η5-C5H3R)2(SiMe2)]Mo2(CO)6 (3, rac-7), or both GeMe2 and SiMe2 are cleaved to afford the nonbridged products [(η5-C5H4R)Mo(CO)3]2 (2, 6). The reactions also produce germylidyne trimolybdenum clusters [(η5-C5H3R)2(SiMe2)](η5-C5H4R)[Mo(CO)2]3(μ3-GeMe) (4, rac-/meso-7) containing the Mo3(μ3-GeMe) units. Similarly, reaction of the single GeMe2-bridged dicyclopentadienes (C5H5)2GeMe2 (9) with Mo(CO)6 also results in the degermylated 2, as well as the similar trimolybdenum cluster [(η5-C5H5)Mo(CO)2]3(μ3-GeMe) (10). The molecular structures of 4 and trans-5 were determined by X-ray diffraction. 相似文献
11.
M. N. Sokolov E. V. Chubarova E. V. Peresypkina A. V. Virovets V. P. Fedin 《Russian Chemical Bulletin》2007,56(2):220-224
The reactions of the tetranuclear hydroxo complexes [M4(μ2-OH)8(H2O)16]8+ (M = Zr or Hf) with the lacunary Keggin-type ([α-PW11O39]7−) and Dawson-type ([α 2-P2W17O61]10−) phosphotungstates in aqueous solutions produce the sandwich polyoxometalate complexes [M(α-PW11O39)2]10− (M = Zr (1) or Hf (2)) and [M(α 2-P2W17O61)2]16− (M = Zr (3) and Hf (4)). The complexes were isolated and structurally characterized as salts with potassium and dimethylammonium cations. The zirconium
and hafnium atoms have a square antiprismatic coordination environment (coordination number is 8). In all complexes, the mutual
arrangement of the ligands corresponds to the syn isomer. Hafnium complexes 2 and 4 are the first structurally characterized polyoxometalate complexes of this metal. The structures of the resulting compounds
were confirmed also by 31P NMR spectroscopy in solution.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 214–218, February, 2007. 相似文献
12.
Ana María Atria Gino Corsini Lissette González Maria Teresa Garland Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(7):m241-m245
catena-Poly[[tetraaquabis(1H-pyrazole-κN2)nickel(II)] [[diaquabis(1H-pyrazole-κN2)nickel(II)]-μ-benzene-1,2,4,5-tetracarboxylato-κ2O1:O4] tetrahydrate], {[Ni(C3H4N2)2(H2O)4][Ni(C10H2O8)(C3H4N2)2(H2O)2]·4H2O}n, (I), and poly[[(μ4-benzene-1,2,4,5-tetracarboxylato-κ4O1:O2:O4:O5)octakis(1H-pyrazole-κN2)dicobalt(II)] tetrahydrate], {[Co2(C10H2O8)(C3H4N2)8]·4H2O}n, (II), are polymeric compounds crystallizing in the space group P, with two independent metallic cations and one benzene-1,2,4,5-tetracarboxylate (btc) anion, each lying on symmetry centres. Individual coordination polyhedra are regular and the main differences are in the way the btc anion binds [μ2 in (I) and μ4 in (II)], promoting a `chain-like' one-dimensional structure in (I) and a `sieve-like' two-dimensional motif in (II). 相似文献
13.
Peter Švančárek Peter Schwendt Jozef Tatiersky Ivana Smatanová Jaromír Marek 《Monatshefte für Chemie / Chemical Monthly》2000,131(2):145-154
Summary. Oxo peroxo glycolato complexes of vanadium(V) (M
2[V2O2(O2)2(C2H2O3)2]ċnH2O (n=0, 1; M=NBu4
+ (1), K+ (2), NH4
+ (3), Cs+ (4), NPr4
+ (5)) as well as (NBu4)2[V2O4(C2H2O3)2]ċ H2O (6) have been prepared and characterized by spectroscopic methods. X-Ray structure analysis of 1 revealed the presence of dinuclear [V2O2(O2)2(C2H2O3)2]2− anions with a (chemical structure) bridging core and six coordinated vanadium(V) atoms in a distorted pentagonal pyramidal
array.
Received July 12, 1999. Accepted (revised) October 28, 1999 相似文献
14.
Peter ?van?árek Peter Schwendt Jozef Tatiersky Ivana Smatanová Jaromír Marek 《Monatshefte für Chemie / Chemical Monthly》2000,35(4):145-154
Oxo peroxo glycolato complexes of vanadium(V) (M 2[V2O2(O2)2(C2H2O3)2]ċnH2O (n=0, 1; M=NBu4 + (1), K+ (2), NH4 + (3), Cs+ (4), NPr4 + (5)) as well as (NBu4)2[V2O4(C2H2O3)2]ċ H2O (6) have been prepared and characterized by spectroscopic methods. X-Ray structure analysis of 1 revealed the presence of dinuclear [V2O2(O2)2(C2H2O3)2]2− anions with a (chemical structure) bridging core and six coordinated vanadium(V) atoms in a distorted pentagonal pyramidal array. 相似文献
15.
《Journal of Coordination Chemistry》2012,65(19):3252-3269
The reaction of [(η5-C5Me5)M(μCl)Cl]2 with the ligand (L∩L) in the presence of sodium methoxide yielded compounds of general formula [(η5-C5Me5)M(L∩L)Cl] (1–10) (where M = Ir or Rh and L∩L = N∩O or O∩O chelate ligands). Azido complexes of formulation [(η5-C5Me5)M(L∩L)N3] (11–20) have been prepared by the reaction of [(η5-C5Me5)M(μN3)(X)]2 (X = Cl or N3) with the corresponding ligands or by the direct reaction of [(η5-C5Me5)M(L∩L)Cl] with NaN3. These azido complexes [(η5-C5Me5)M(L∩L)N3] undergo 1,3-dipolar cycloaddition reaction with substituted alkynes in CH2Cl2 and for the first time in ethanol at room temperature to yield iridium (III) and rhodium (III) triazoles (21–28). The compounds were characterized on the basis of spectroscopic data, and the molecular structures of 2 and 26 have been established by single crystal X-ray diffraction. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(8):1405-1415
Treatment of [RuCl2(PPh3)3] with 2 equiv. HimtMPh (HimtMPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-[Ru(κ 2-S,N-imtMPh)2(PPh3)2] (1), while interaction of [RuCl2(PPh3)3] and 2 equiv. HimtMPh in tetrahydrofuran (THF) without base gave [RuCl2(κ 1-S-HimtMPh)2(PPh3)2] (2). Treatment of [RuHCl(CO)(PPh3)3] with 1 equiv. HimtMPh in THF gave [RuHCl(κ 1-S-HimtMPh)(CO)(PPh3)2] (3), whereas reaction of [RuHCl(CO)(PPh3)3] with 1 equiv. of the deprotonated [imtMPh]? or [imtNPh]? (imtNPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave [RuH(κ 2-S,N-imtRPh)(CO)(PPh3)2] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes [RuCl(κ 2-S,N-imtMPh)(CO)(PPh3)2] (5a) and [RuCl(κ 2-S,N-imtNPh)(CO)(PPh3)2] (5b), respectively, in refluxing CHCl3 by chloride substitution of the RuH. Photolysis of 5a in CHCl3 at room temperature afforded an oxidized product [RuCl2(κ 2-S,N-imtMPh)(PPh3)2] (6). Reaction of 6 with excess [imtMPh]? afforded 1. The molecular structures of 1·EtOH, 3·C6H14, 4b·0.25CH3COCH3, and 6·2CH2Cl2 have been determined by single-crystal X-ray crystallography. 相似文献
17.
《Journal of Coordination Chemistry》2012,65(12):2054-2064
Two iron(II) complexes, [FeII(pytBuN3)2](FeCl4) (1) and [FeII(pytBuMe2N3)Cl2] (2), with sterically constrained pytBuN3 and pytBuMe2N3 chelate ligands (pytBuN3 = 2,6-bis-(aldiimino)pyridyl; pytBuMe2N3 = 2,6-bis-(ketimino)pyridyl), have been synthesized and characterized by elemental analysis, IR, UV–vis spectra, and preliminary X-ray single-crystal diffraction. The latter revealed that Fe(II) in 1 is six-coordinate by six nitrogen donors from two bisiminopyridines in a distorted octahedron. Complex 2 reacts with thiourea with a second-order rate constant k2 = (2.50 ± 0.05) × 10?3 M?1 s?1 at 296 K, and the reaction seemed to be slow. In a similar way, the interaction of 2 and DNA was studied by fluorescence and absorption spectroscopy. The results revealed that 2 caused fluorescence quenching of DNA through a dynamic quenching procedure. The binding constants KA, Kapp, and KSV as well as the number of binding sites between 2 and DNA were determined. 相似文献
18.
《Journal of Coordination Chemistry》2012,65(10):1069-1087
The mono(pentamethylcyclopentadienyl) lanthanide complexes [(C5Me5)Yb(μ-I)(μ-η 5?: η 5-C5Me5)Yb(C5Me5)]n (1), {[(C5Me5)Sm]3(μ-Cl)4(μ 3-Cl)(μ 3-OH)(THF)}2 (2), {[(C5Me5)Sm]2 (μ-OH)(μ-Cl)4(μ 3-Cl)Mg(THF)2}2 (3), [(C5Me5)2Sm](μ-Cl)6(μ 3-Cl)2(μ 4-Cl)[(C5Me5)Sm]4 (4), {[(C5Me5)Nd]3(μ 3-Cl)4(μ 4-Cl)2(μ 3-O2CPh)2K2(η 6-C7H8)}2 (5), [(C5Me5)Nd(C8H8)]2(μ-dioxane) (6), [(C5Me5)Yb(MeOtBu)]2(μ-η 8?:?η 8-C8H8) (7), [(C5Me5)Dy(μ-I)2]3 (8), and [(C5Me5) Tm(MeCN)6]I2 (9), have been identified by X-ray crystallography. 1 is unusual in that it has a μ-η 5?:?η 5-C5Me5 ring that generates a local bent metallocene environment around ytterbium. Complexes 2–5 demonstrate the versatility of bridging chlorides in generating a variety of structures for mono(pentamethylcyclopentadienyl) lanthanide halides. Complex 6 shows how dioxane can generate a crystallographically-analyzable complex by bridging two mixed-ligand metallocene units that do not readily crystallize with THF. The structure of 7 shows how methyl tert-butyl ether (MTBE) ligates a lanthanide. Complex 8 is a trimeric cyclopentadienyl lanthanide halide unusual in that it has six bridging halides that roughly define a trigonal prism. Complex 9 constitutes an organometallic example of a lanthanide in which acetonitrile completely displaces iodide counterions. 相似文献
19.
《Journal of Coordination Chemistry》2012,65(23):4131-4143
Two copper(II) complexes, [Cu2(μ-benzoato)(L1)2]NO3·2H2O (1) and [Cu2(μ-succinato)(L2)2(H2O)]ClO4 (2), have been synthesized, where L1 = N′-[(E)-phenyl(pyridin-2-yl)methylidene]benzoylhydrazone and L2 = N′-[(E)-pyridin-2-ylmethylidene]benzoylhydrazone. These complexes were characterized including by single-crystal X-ray diffraction studies. The copper is five-coordinate in 1 while in 2 one copper is five-coordinate and the other is six-coordinate. Electrochemical behavior of these complexes was measured by cyclic voltammetry. The conproportionation equilibrium constants (Kcon) for both complexes have been estimated. The superoxide dismutase (SOD) activities of 1 and 2 were measured by nitro blue tetrazolium assay. Complex 1 has better SOD activity than 2. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(22):4055-4069
Two new N2O2 unsymmetrical Schiff bases, H2L1 = 3-[({o-[(E)-(o-hydroxyphenyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol and H2L2 = 3-[({o-[(E)-(2-hydroxy-1-naphthyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol, and their copper(II) and nickel(II) complexes, [CuL1] (1), [CuL2] (2), [NiL1] (3), and [NiL2] (4), have been synthesized and characterized by elemental analyses and spectroscopic methods. The crystal structures of these complexes have been determined by X-ray diffraction. The coordination geometry around Cu(II) and Ni(II) centers is described as distorted square planar in all complexes with the CuN2O2 coordination more distorted than the Ni ones. The electrochemical studies of these complexes indicate a good correlation between the structural distortion and the redox potentials of the metal centers. The ligand and metal complexes were also screened for their in vitro antibacterial activity. 相似文献