共查询到20条相似文献,搜索用时 31 毫秒
1.
David J. Harding Phimphaka Harding Jutaporn Kivnang Harry Adams 《Transition Metal Chemistry》2010,35(5):521-526
The cationic complexes, [TpRNi(bpym)]+ {TpR = tris(3,5-diphenylpyrazolyl)borate, R = Ph2
1; tris(3-phenyl-5-methylpyrazolyl)borate, R = Ph,Me 2} were synthesized by reacting [TpRNiBr] (R = Ph2; Ph,Me) with bipyrimidine followed by subsequent addition of KPF6 in CH2Cl2. The green solids have been characterized by IR, UV–Vis and 1H NMR spectroscopy. Crystallographic studies of [TpPh,MeNi(bpym)]PF6 reveal a five-coordinate square pyramidal nickel centre with a κ3-coordinated TpPh,Me ligand and a chelating bipyrimidine ligand. Cyclic voltammetric studies show irreversible reduction with the degree of reversibility dependent on the type of TpR ligand. 相似文献
2.
Mixed ligand tris(pyrazolyl)borate and β-diketonate complexes have been prepared by reacting [TpPh2NiBr] with a β-diketone and then adding 1,8-diazabicycloundec-7-ene to yield [TpPh2Ni(β-dkt)] {β-dkt = hexafluoroacetylacetonate (hfac) 1, phenylbutanedionate (pbd) 2, diphenylpropanedionate (dbm) 3, tetramethylheptanedionate (tmhd) 4}. The green solids have been characterized by IR, UV–Vis, and 1H NMR spectroscopy. Crystallographic studies of [TpPh2Ni(dbm)] reveal a five-coordinate, square pyramidal nickel centre with a κ3-coordinated TpPh2 ligand and a bidentate β-diketonate ligand. 相似文献
3.
A [{hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate}(3-phenyl-5-methyl-pyrazole) nickel chloride] [TpPh,MeNi(Cl)PzPh,MeH] (I) has been synthesized and explored as ionophores for the preparation of a poly (vinyl chloride) (PVC) membrane sensor for azide and thiocyanate anions. The compounds [TpPh,MeNi(N3)PzPh,MeH] (II) and [TpPh,MeNi(SCN)PzPh,MeH] (III) were characterized by their crystal structures and proved to be bonded as monodentate through nitrogen atom of azide and thiocyanate anion. Potentiometric investigations also indicate high affinity of this receptor for thiocyanate and azide ions. PVC based membranes of I using as hexadecyltrimethylammonium bromide (HTAB) cation discriminator and o-nitrophenyloctyl ether (o-NPOE), dibutylphthalate (DBP), acetophenone (AP) and tributylphosphate (TBP) as plasticizing solvent mediators were prepared and investigated as SCN− and N3− selective sensors. The best performance was shown by the membrane of thiocyanate with composition (w/w) of (I) (7%):PVC (31%):DBP (60%):HTAB (2%). This sensor works well over a wide concentration range 5.3 × 10−7 to 1.0 × 10−2 M with Nernstian compliance (59.2 mV decade−1 of activity) within pH range 2.5-9.0 with a response time of 11 s and showed good selectivity for thiocyanate ion over a number of anions. The sensor exhibits adequate life (3 months) and could be used successfully for the determination of thiocyanate content in human urine, saliva and river water samples. While the membrane of [TpPh,MeNi(Cl)PzPh,MeH] ionophore with composition (I) (6%):HTAB (4%):PVC (31%):TBP (59%) showed highest sensitivity and widest linear range for azide ion. These sensors exhibit the maximum working concentration range of 8.1 × 10−6 to 1.0 × 10−2 M with Nernstian slope of 59.3 mV decade−1 of activity. It can be applied for the monitoring of the azide ions concentration in aqueous black tea and orange juice samples. 相似文献
4.
The complex [TpPh,MeNi(Cl)PzPh,MeH] ( I ) [TpPh,Me=hydrotris(3‐phenyl‐5‐methyl‐pyrazol‐1‐yl)borate; PzPh,MeH=3‐phenyl‐5‐methyl‐pyrazole] has been synthesized and explored as ionophore for the preparation of a poly(vinyl chloride) (PVC) membrane sensor for benzoate anions. The formation constants for the interaction of complex I with different organic/inorganic anions in solution have also been studied by sandwich membrane method. PVC based membranes of I using tridodecylmethylammonium chloride (TDDMACl) as cation discriminator and o‐nitrophenyloctyl ether (o‐NPOE), dibutylphthalate (DBP), benzylacetate (BA) and tributylphosphate (TBP) as plasticizing solvent mediators were prepared and investigated as benzoate selective sensors. The best performance was shown by the membrane with composition (w/w) of I (5): PVC (150): NPOE (345): TDDMACl (0.3). The proposed sensor exhibits significantly enhanced selectivity toward benzoate ions over the concentration range 2.2×10?6–1.0×10?1 M with a lower detection limit of 1.4×10?6 M and a Nernstian slope of 59.2 mVdecade?1 of activity within a pH range of 4.5–8.5. The sensor has a response time of 12 s and can be used for at least 8 weeks without any considerable divergence in their potential response. The membrane sensor of complex I have been checked for reversible and accurate sensing of benzoate levels present in liquid food products. 相似文献
5.
[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]M (M = K, Tl) reacts with “GaI” to give a series of compounds that feature Ga–Ga bonds, namely [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaI3, [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]GaGaI2GaI2(
\textHpz\textMe2 {\text{Hpz}}^{{{\text{Me}}_{2} }} ) and [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga(GaI2)2Ga[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ], in addition to the cationic, mononuclear Ga(III) complex {[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]2Ga}+. Likewise, [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]M (M = K, Tl) reacts with (HGaCl2)
2
and Ga[GaCl4] to give [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaCl3, {[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]2Ga}[GaCl4], and {[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]GaGa[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]}[GaCl4]2. The adduct [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→B(C6F5)3 may be obtained via treatment of [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]K with “GaI” followed by addition of B(C6F5)3. Comparison of the deviation from planarity of the GaY3 ligands in [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaY3 (Y = Cl, I) and [
\textTm\textBu\textt {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga→GaY3, as evaluated by the sum of the Y–Ga–Y bond angles, Σ(Y–Ga–Y), indicates that the [
\textTm\textBu\textt {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga moiety is a marginally better donor than [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga. In contrast, the displacement from planarity for the B(C6F5)3 ligand of [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→B(C6F5)3 is greater than that of [
\textTm\textBu\textt {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga→B(C6F5)3, an observation that is interpreted in terms of interligand steric interactions in the former complex compressing the C–B–C
bond angles. 相似文献
6.
Arto Valkonen Katri Laihia Erkki Kolehmainen Reijo Kauppinen Pál Perjési 《Structural chemistry》2012,23(1):209-217
1H and 13C NMR chemical shifts have been determined and assigned based on PFG 1H, 13C HMQC, and HMBC experiments for 3-(4′-X-benzyl)-4-chromenones (Ia, X = CN and Ib, X = NO2), 3-(4′-X-benzyl)-4-thiochromenones (IIa, X = Cl and IIb, X = Br), (E)-3-(4′-X-benzylidene)-4-chromanones (IIIa–IIIe, X = OCH3, CH3, Cl, N(CH3)2, Br), (Z)-3-(4′-X-benzylidene)4-thiochromanones (IVa–IVd, X = Cl, Br, F, OCH3), 2-benzyl-1,2,3,4-tetrahydro-1-naphthol (V), 2-benzyl- and (E)-2-benzylidene-1-tetralones (VI and VII), and (E)-2-benzylidene-1-benzosuberol (VIII). The crystal structures have been determined for the following seven compounds: derivatives of 4-chromanones (IIIa–IIId), 1-tetrahydronaphtol (V), and 1-tetralones (VI and VII). The molecular features and intermolecular interactions in crystal state have been discussed. 相似文献
7.
Zhi-Hong Ma Ming-Xia Zhao Fang Li Hong Wang Xue-Zhong Zheng Jin Lin 《Transition Metal Chemistry》2010,35(4):387-391
Cyclopentadienes (C5Me4R) [R = Allyl (1), n-Butyl (2), Benzyl (3), and PhMe-2 (4)] reacted with Fe(CO)5 in refluxing xylene to give new substituted tetramethylcyclopentadienyl dinuclear iron carbonyl complexes [(η
5-C5Me4R)Fe(CO)(μ-CO)]2 [R = Allyl (5), n-Butyl (6), Benzyl (7), and PhMe-2 (8)], respectively. The four new complexes 5–8 were characterized by elemental analysis, IR, and 1H NMR spectra. The crystal structures of complexes 5–7 were determined using single crystal X-ray diffraction. The crystal structure of complex 5 showed that allyl underwent isomerization to give the corresponding methyl-vinyl. A possible mechanism is discussed. The
X-ray crystal structures of complexes 5, 6, and 7 confirm the structure with bridging and terminal CO groups. They show that the steric effects of substituents influence the
Fe–Fe bond distances of the complexes. 相似文献
8.
Shafqat Nadeem Muhammad Khawar Rauf Saeed Ahmad Masahiro Ebihara Syed Ahmed Tirmizi Sarfaraz Ahmed Bashir Amin Badshah 《Transition Metal Chemistry》2009,34(2):197-202
Palladium(II) complexes of thiones having the general formula [Pd(L)4]Cl2, where L = thiourea (Tu), methylthiourea (Metu), N,N′-dimethylthiourea (Dmtu), and tetramethylthiourea (Tmtu) were prepared by reacting K2[PdCl4] with the corresponding thiones. The complexes have been characterized by elemental analysis, IR and NMR spectroscopy, and
two of these, [Pd(Dmtu)4]Cl2 · 2H2O (1) and [Pd(Tmtu)4]Cl2 (2), by X-ray crystallography. An upfield shift in the >C=S resonance of thiones in 13C NMR and downfield shift in N–H resonance in 1H NMR are consistent in showing sulfur coordination with palladium(II). The crystal structures of the complexes show a square-planar
coordination environment around the Pd(II) ions with the average cis and trans S–Pd–S bond angles of 89.64° and 173.48°, respectively.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
An erratum to this article can be found at 相似文献
9.
The ortho-metalated complex [Pd(x){κ
2
(C,N)-[C6H4CH2NRR′ (Y)}] (2a–4a and 2b–3b) was prepared by refluxing in benzene equimolecular amounts of Pd(OAc)2 and secondary benzylamine [a, EtNHCH2Ph; b, t-BuNHCH2Ph followed by addition of excess NaCl. The reaction of the complexes [Pd(x){κ
2
(C,N)-[C6H4CH2NRR′ (Y)}] (2a–4a and 2b–3b) with a stoichiometric amount of Ph3P=C(H)COC6H4-4-Z (Z = Br, Ph) (ZBPPY) (1:1 molar ratio), in THF at low temperature, gives the cationic derivatives [Pd(OC(Z-4-C6H4C=CHPPh3){κ
2
(C,N)-[C6H4CH2NRR′(Y)}] (5a–9a, 4b–6b, and 4b′–6b′), in which the ylide ligand is O-coordinated to the Pd(II) center and trans to the ortho-metalated C(6)H(4) group, in an “end-on
carbonyl”. Ortho-metallation, ylide O-coordination, and C-coordination in complexes (5a–9a, 4b–6b, and 4b′–6b′) were characterized by elemental analysis as well as various spectroscopic techniques. 相似文献
10.
Verena M. Birkelbach Dr. Renita Thim Dr. Christoph Stuhl Dr. Cäcilia Maichle-Mössmer Prof. Dr. Reiner Anwander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(64):14711-14720
A series of solvent-free heteroleptic terminal rare-earth-metal alkyl complexes stabilized by a superbulky tris(pyrazolyl)borato ligand with the general formula [TptBu,MeLnMeR] have been synthesized and fully characterized. Treatment of the heterobimetallic mixed methyl/tetramethylaluminate compounds [TptBu,MeLnMe(AlMe4)] (Ln=Y, Lu) with two equivalents of the mild halogenido transfer reagents SiMe3X (X=Cl, I) gave [TptBu,MeLnX2] in high yields. The addition of only one equivalent of SiMe3Cl to [TptBu,MeLuMe(AlMe4)] selectively afforded the desired mixed methyl/chloride complex [TptBu,MeLuMeCl]. Further reactivity studies of [TptBu,MeLuMeCl] with LiR or KR (R=CH2Ph, CH2SiMe3) through salt metathesis led to the monomeric mixed-alkyl derivatives [TptBu,MeLuMe(CH2SiMe3)] and [TptBu,MeLuMe(CH2Ph)], respectively, in good yields. The SiMe4 elimination protocols were also applicable when using SiMe3X featuring more weakly coordinating moieties (here X=OTf, NTf2). X-ray structure analyses of this diverse set of new [TptBu,MeLnMeR/X] compounds were performed to reveal any electronic and steric effects of the varying monoanionic ligands R and X, including exact cone-angle calculations of the tridentate tris(pyrazolyl)borato ligand. Deeper insights into the reactivity of these potential precursors for terminal alkylidene rare-earth-metal complexes were gained through NMR spectroscopic studies. 相似文献
11.
Some mixed ligand complexes of the type [M(L)(en or phen)(X)2]; where M = Mn(II), Co(II) or Ni(II); L = 2-phenyl-3-(benzylamino)-1,2-dihydroquinazolin-4(3H)-one; en = ethylenediamine, phen = 1,10-phenanthroline; X = N3
− or NCS− have been prepared. All the complexes were characterized by physico-chemical, spectroscopic and thermal studies. On the basis
of electronic spectra and magnetic susceptibility measurements, an octahedral geometry has been proposed for all the complexes.
The phen complexes are thermally more stable than the en complexes. The electrochemical behavior of the Ni(II) complexes showed that the complexes of phen are reduced at more positive potential compared to the corresponding en complexes. 相似文献
12.
The DFT-B3LYP and G3X model chemistry were used to predict the cation structures and energetics of fluorinated, chlorinated,
and brominated methanes. Ion–complex structures between methylene cations and HX (X = F, Cl, Br) were found for all H-containing
cations, and [CHF–FH]+, [CF2–FH]+, [CCl2–ClH]+, and [CCl2–FH]+ structures are more stable than their normal tetravalent structures. Several cations should also be better described as ion–complex
structures between methyl cations and halogen atoms, e.g., [CF3–Br]+. Transition states connecting normal and ion–complex structures were also located, and potential energy diagrams were constructed
for decomposition of methane cations and to predict the fragmentation pathways. The G3X energies were used to predict the
adiabatic ionization energies (IEas) and ion fragment appearance energies (AEs) from methanes. Many of the experimental AEs correspond to the energies of transition
states instead of the thermodynamic dissociation limits.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
13.
Tietz T Limberg C Stösser R Ziemer B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(36):10010-10020
A series of complexes of the type [(TpR1,R2)M(X)] (Tp=trispyrazolylborato) with R1/R2 combinations Me/tBu, Ph/Me, iPr/iPr, Me/Me and for M=Mn or Fe coordinating [PzMe,tBu]? (Pz=pyrazolato) or Cl? as co‐ligand X has been synthesised. Although the chloride complexes were very unreactive and stable in air, the pyrazolato series was far more reactive in contact with oxidants like O2 and tBuOOH. The [(TpR1,R2)M(PzMe,tBu)] complexes proved to be active pre‐catalysts for the oxidation of cyclohexene with tBuOOH, reaching turnover frequencies (TOFs) ranging between moderate and good in comparison to other manganese catalysts. Cyclohexene‐3‐one and cyclohexene‐3‐ol were always found to represent the main products, with cyclohexene oxide occasionally formed as a side product. The ratios of the different oxidation products varied with the reaction conditions: in the case of a peroxide/alkene ratio of 4:1, considerably more ketone than alcohol was obtained and cyclohexene oxide formation was almost negligible, whereas a ratio of 1:10 led to a significant increase of the alcohol proportion and to the formation of at least small amounts of the epoxide. Pre‐treatment of the dissolved [(TpR1,R2)M(PzMe,tBu)] pre‐catalysts with O2 led to product distributions and TOFs that were very similar to those found in the absence of O2, so that it may be argued that tBuOOH and O2 both lead to the same active species. The results of EPR spectroscopy and ESI‐MS suggest that the initial product of the reaction of [(TpMe,Me)Mn(PzMe,tBu)] with O2 contains a MnIII(O)2MnIV core. Prolonged exposure to O2 leads to a different dinuclear complex containing three O‐bridges and resulting in different TOFs/product distributions. Analogous findings were made for other complexes and formation of these overoxidised products may explain the deviation of the catalytic performances if the reactions are carried out in an O2 atmosphere. 相似文献
14.
Abstract Photochemical reaction of methanol solution containing 1,4-diferrocenyl- or 1,4-diphenyl-1,3-butadiynes and iron pentacarbonyl
into which CO was constantly bubbled, yielded diiron hexacarbonyl complexes of cumulene ligand systems, [η1: η3-{RCHC2CR(COOMe)}Fe2(CO)6] (1; E, R = Fc,
2; Z, R = Fc, 5; E, R = Ph,
6; Z, R = Ph) and [η3: η3-{RCHC2CR(COOMe)}Fe2(CO)6] (3; E, R = Fc, 7; E, R = Ph), formed by 1,4-addition of –COOMe and –H to the butadiynes. Additionally, diferrole, [Fe(CO)4{C(O)CC(Fc)C(O)}2],4 was obtained in minor quantity. Compounds 1, 2, 5 and 6 contain vinylallyl carbon framework which is stabilized by MeOC=O → Fe bond along with η1: η3 coordinated Fe2(CO)6 unit. Compounds 3 and 7 contain butatriene units which are stabilized by η3: η3 coordinated Fe2(CO)6 unit. Characterization of the new compounds was carried out by IR and 1H and 13C NMR spectroscopy and by mass spectrometry. Molecular structures of 2–7 were established by single crystal X-ray diffraction methods.
Graphical Abstract Diiron hexacarbonyl complexes of cumulene ligand systems, [η1: η3 {RCHC2CR(COOMe)}] (1; E, R = Fc, 2; Z, R = Fc, 5; E, R = Ph,
6; Z, R = Ph) and [η3: η3-{RCHC2CR(COOMe)}] (3; E, R = Fc,
7; E, R = Ph) were obtained from photochemical reactions between Fe(CO)5, CO and methanol. Yield of the minor product, the diferrole, 4, was improved when the photoreaction was carried out in hexane in place of methanol
相似文献
15.
Sumitava Khan Subhasis Roy Kishalay Bhar Partha Mitra Alexandra M. Z. Slawin Barindra Kumar Ghosh 《Transition Metal Chemistry》2011,36(1):99-106
Two hexacoordinated mononuclear Co(III) compounds of the type cis-[Co(L)(N3)2] X [1, X = ClO4; 2, X = PF6; L = N,N′-(bis(pyridine-2-yl)benzylidine)-1,4-butanediamine] have been synthesized and characterized by physicochemical and spectroscopic
methods. The crystal structures of complexes 1 and 2 both have distorted octahedral geometry with two terminal azides in mutual cis orientations. In the crystalline state, two
mononuclear units of 1 are associated by weak C–H…π interactions to produce a dimeric unit, which packs through C–H…O hydrogen bonds and π…π interactions
leading to a 2-D continuum. The mononuclear units in 2 are engaged in weak cooperative intermolecular C–H…π interactions and multiple C–H…F hydrogen bonds giving rise to a 3-D
network structure. These diamagnetic compounds are redox active and show luminescence in DMF solutions. 相似文献
16.
V. V. Sharutin V. S. Senchurin O. K. Sharutina B. B. Kunkurdonova 《Russian Journal of Inorganic Chemistry》2011,56(9):1384-1389
Complexes [Me3EtN]2+[CoI4]2− (I) and [Me3EtN]2+[CoI4]2− (II) were synthesized by reacting trimethylalkylammonium iodide with cobalt(II) iodide in acetone. According to X-ray diffraction
data, complexes I and II consist of tetrahedral tetraalkylammonium cations (for I, N-C is 1.481(5)–1.590(8) CNC is 107.3(3)°–111.6(3)°; for II, N-C is 1.485(8)–1.506(10) ? and CNC is 106.9(7)°–111.7(5)°) and [CoI4]2− anions (for I, Co-I is 2.5951(5)–2.6127(5) ? and ICoI is 104.67(2)°–113.23(2)°; for II, Co-I is 2.5914(8)–2.5943(9) ? and ICoI is 107.05(2)°–114.42(5)°). 相似文献
17.
Dr. Qing You Prof. Dr. Jie Zhang Prof. Dr. Xigeng Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(34):7702-7710
A new method for the modification of a silylamino ligand has been developed through mono and dual C(sp3)−H/Si−H cross-dehydrocoupling with silanes. The reaction of [LY{η2-(C,N)-CH2Si(Me2)NSiMe3}] (L=bis(2,6-diisopropylphenyl)-β-diketiminato, L′ ( 1L ′); L=tris(3,5-dimethylpyrazolyl)borate, TpMe2 ( 1TpMe2 )) with 2 equivalents of PhSiH3 in toluene gave the complexes [LY{η2-(C,N)-C(SiH2Ph)2Si(Me2)NSiMe3}] (L=L′ ( 2L’ ); L=TpMe2 ( 2TpMe2 )). Moreover, 1TpMe2 reacted with the secondary silanes Ph2SiH2 and Et2SiH2 to afford the corresponding mono C−H activation products [TpMe2Y{η2-(C,N)-CH(SiHR2)Si(Me2)NSiMe3}] (R=Ph ( 4 b ); R=Et ( 4 c )). The equimolar reaction of 1TpMe2 with PhSiH3 also produced the mono C−H activation product 4 a ([TpMe2Y{η2-(C,N)-CH(SiH2Ph)Si(Me2)NSiMe3}(thf)]). A study of their reactivity showed that 4 a facilely reacted with 2 equivalents of benzothiazole by an unusual 1,1-addition of the C=N bond of the benzothiazolyl unit to the Si−H bond to give the C−H/Si−H cross-dehydrocoupling product [(TpMe2)Y{η3-(N,N,N)-N(SiMe3)SiMe2CH2Si(Ph)(CSC6H4N)(CHSC6H4N)}] ( 5 ). These results indicate that this modification endows the silylamino ligand with novel reactivity. 相似文献
18.
Diacetylplatinum(II) complexes [Pt(COMe)2(N^N)] (N^N = bpy, 3a; 4,4′-t-Bu2-bpy, 3b) were found to undergo oxidative addition reactions with organyl halides. The reaction of 3a with methyl iodide and propargyl bromide led to the formation of the cis addition products (OC-6-34)-[Pt(COMe)2(R)X(bpy)] (R = Me, X = I, 4a; CH2C≡CH, X = Br, 4k). Analogous reactions of 3a with ethyl iodide, benzyl bromide, and substituted benzyl bromides, 3-(bromomethyl)pyridine, 2-(bromomethyl)thiophene, allyl
bromide, and cyclohex-2-enyl bromide led to exclusive formation of the trans addition products (OC-6-43)-[Pt(COMe)2(R)X(bpy)] (X = I, R = Et, 4b; X = Br, R = CH2C6H5, 4c; CH2C6H4(o-Br), 4d; CH2C6H4(p-COOH), 4e; CH2-3-py (3-pyridylmethyl), 4f; CH2-2-tp (2-thiophenylmethyl), 4g; CH2CH=CH2, 4h; c-hex-2-enyl (cyclohex-2-enyl), 4i). All complexes 4 were characterized by microanalysis, 1H and 13C NMR and IR spectroscopy. Additionally, complexes 4a, 4f, and 4g were characterized by single-crystal X-ray diffraction analyses. Reactions of 3a and 3b with o-, m- and p-bis(bromomethyl)benzene, respectively, led to the formation of dinuclear platinum(IV) complexes [{Pt(COMe)2Br(N^N)}2-{μ-(CH2)2C6H4}] (5). These complexes were characterized by microanalysis, IR spectroscopy, and depending on their solubility by 1H and 13C NMR spectroscopy, too. A single-crystal X-ray diffraction analysis of complex [{Pt(COMe)2Br(bpy)}2{μ-m-(CH2)2C6H4}] (5b) confirmed its dinuclear composition. The solid-state structures of 4a, 4f, 4g, and 5b are discussed in terms of C–H···O and O–H···O hydrogen bonds as well as π–π stacking between aromatic rings. 相似文献
19.
Sahra C. Lemos Silmar J. S. Franchi Adelino V. G. Netto Antonio E. Mauro Oswaldo Treu-Filho Regina C. G. Frem Eduardo Tonon de Almeida Cláudia Torres 《Journal of Thermal Analysis and Calorimetry》2011,106(2):391-397
This work describes the synthesis, characterization, and the thermal behavior investigation of four palladium(II) complexes
with general formulae [PdX2(mba)2], in which mba = N-methylbenzylamine and X = OAc− (1), Cl− (2), Br− (3) or I− (4). The complexes were characterized by elemental analysis, infrared vibrational spectroscopy, and 1H nuclear magnetic resonance. The stoichiometry of the complexes was established by means of elemental analysis and thermogravimetry
(TG). TG/DTA curves showed that the thermodecomposition of the four complexes occurred in 3–4 steps, leading to metallic palladium
as final residue. The palladium content found in all curves was in agreement with the mass percentages calculated for the
complexes. The following thermal stability sequence was found: 3 > 2 > 4 > 1. The geometry optimization of 1, 2, 3, and 4, calculated using the DFT/B3LYP method, yielded a slightly distorted square planar environment around the Pd(II) ion made
by two anionic groups and two nitrogen atoms from the mba ligand (N1 and N2), in a trans-relationship. 相似文献
20.
Manganese complexes of the type [TpMn(X)] and [TpMn(μ-N3)(μ-X)MnTp] (X = acetylacetonate, acac; picolinate, pic and Tp = TpPh,Me for acac, Tp = Tpipr2 for pic complexes) having TpPh,Me (hydrotris(3-phenyl,5-methyl-pyrazol-1-yl)borate)/Tpipr2 (hydrotris(3,5-diisopropyl-pyrazol-1-yl)borate) as a supporting ligand have been synthesized and structurally characterized. IR and X-ray structures suggest that complexes 7 and 9 are binuclear with azido and bidentate ligands (acac/pic) bridging, whereas complexes 6 and 8 are mononuclear with a 5-coordinated metal center. In complex 9 the picolinate is coordinated as tridentate in a η3-fashion, but in complex 7 acac behaves as bidentate, whereas azide is coordinated in a bridging bidentate μ-1,3-manner in both 7 and 9. Since the coordination geometry of the manganese ions in complex 9 is very similar to the active site structure of manganese-containing pseudocatalase, we have tested the catalytic activity of the same towards the disproportionation of hydrogen peroxide. The catalytic results indicated that complex 9 has reasonably good catalase activity and may be suitable, structurally as well as functionally, as a model for the pseudocatalase enzyme. 相似文献