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1.
The reaction of the dinuclear complex Co2(-OOCCMe3)2(2-OOCCMe3)2bpy2 (1) with the polymer [Co(OH) n (OOCCMe3)2–n ] x afforded the unsymmetrical dinuclear complex bpyCo2(2-O,2-OOCCMe3)(2-O,O"-OOCCMe3)2(2-OOCCMe3) (2). The reaction of 2,2"-dipyridylamine with [Co(OH) n (OOCCMe3)2–n ] x gave rise to the analogous complex [(C5H4N)2NH]Co2(2-O,2-OOCCMe3)(-OOCCMe3)2(2-OOCCMe3) (3). The reaction of complex 1 with Ni4(3-OH)2(-OOCCMe3)4(OOCCMe3)2(MeCN)2[2-o-C6H4(NH2)(NHPh)]2 (4) produced an isostructural heterometallic analog of complex 2 with composition bpyM2(2-O,2-OOCCMe3)(2-O,O"-OOCCMe3)2(2-OOCCMe3) (5) (M = Co, Ni; Co : Ni = 1 : 1) and the dinuclear heterometallic complex bpy(HOOCCMe3)M(-OH2)(-OOCCMe3)2M(OOCCMe3)2[o-C6H4(NH2)(NHPh)] (6) (M = Co, Ni; Co : Ni = 0.15 : 1.85). Compounds 2 and 5 exhibit ferromagnetic spin-spin exchange interactions.  相似文献   

2.
Antiferromagnetic Mn(II) polymers of general formula {[L2Mn(μ-OOCCMe3)2][Mn2(μ-OOCCMe3)4]}n (L = 1,2-phenylenediamine (3) and 4,5-dimethyl-1,2-phenylenediamine (4)) were synthesized from [Mn(μ-OOCCMe3)2(HOEt)] n (1) polymer and arenediamines in MeCN solution. The tetranuclear cluster Fe43-OH)2(μ-OOCCMe3)42-OOCCMe3)2(EtOH)6 (5) was prepared by reacting FeSO4·7H2O with KOOCCMe3 in EtOH and was used as starting pivalate iron(II) agent in further reactions. The thermolysis of 5 in MeCN was shown to result in a ferromagnetic polymer [Fe(μ-OOCCMe3)2] n (6) containing tetrahedral iron(II) atoms. Cluster 5 was found to react with o-phenylenediamine giving rise to ferrimagnetic polymer [Fe(μ-OOCCMe3)2(HOEt)]n (7). The reaction 7 with 2,6-diaminopyridine in MeCN results in binuclear antiferromagnetic complex (2,6-(NH2)2C5H3N)2Fe2(μ-OOCCMe3)4· 4MeCN (8). However the reaction of 4,5-dimethyl-1,2-phenylenediamine with polymer 7 yields a polymer {[L2Fe(μ-OOCCMe3)2][Fe2 (μ-OOCCMe3)4]} n (9), which is an analogue of the manganese polymer 4. All newly synthesized compounds were characterized by the by X-ray diffraction studies and magnetic measurement. Dedicated to Professor Ilya I. Moiseev in recognition of his outstanding contribution to cluster chemistry  相似文献   

3.
Three diruthenium carbonyl complexes, namely (η 3:η 5-C5H4C(CH2)2)Ru2(CO)5 (1), (η 3:η 5-C5H4C(CHCH2)(C2H5))Ru2(CO)5 (2), and (η 1:η 5-C5H4C5H8)Ru2(CO)6 (3), were obtained from the reactions of C5H4C(Me)2, C5H4C(Et)2, and C5H4C(CH2)4, respectively, with Ru3(CO)12 in refluxing xylene. The complexes were characterized by elemental analysis, IR and 1H NMR spectra. Single-crystal X-ray diffraction analysis for complexes 1 and 2 revealed that the fulvene ligands bridge two ruthenium atoms in η 3:η 5 fashion.  相似文献   

4.
 Partial removal of chloride anions from the dimer [Pd(η3-2-CH3*C3H4)(μ-Cl)]2 with AgTf(Tf = CF3SO3) followed by addition of dppm affords [Pd23-Me*C3H4)2(μ-Cl)(μ-dppm)]Tf (1). The substitution of Cl by X (X = pz, SC6F5, S py ) using the appropriate salts yields the new derivatives [Pd23-Me*C3H4)2(μ-X)(μ-dppm)]Tf (24). All complexes exhibit a dinuclear half-A-frame structure with two isomers present in solution. The isomers differ in the relative orientation of the two allyl groups (cis or trans). The isomer interconversion was studied by variable temperature 1H NMR spectroscopy. The molecular structures of 2 and 4 were solved by X-ray diffraction studies. A distorted boat conformation of the seven- or six-membered metallacycle was found in both cases.  相似文献   

5.
The thermolysis and reactions of the polymeric high spin MnII and FeII complexes [Mn(μ-OOCBut)2(HOEt)]n (1) and [Fe(μ-OOCBut)2]n (3) with pivalic acid and o-phenylenediamines 1,2-(NH2)2C6H2R2 (R = H or Me) were studied. The synthesis of compound 1 performed with a deficiency of pivalate anions affords the antiferromagnetic chloropivalate polymer { (MeCN)(HOOCBut)(H2O)Mn5Cl(OH)(OOCBut)8·MeCN}n. The reaction of 1 with an excess of pivalic acid produces the antiferromagnetic polymer [Mn4(OOCBut)8(HOOCBut)2]n. The analogous reaction of pivalic acid with polymer 3 gives the mononuclear complex Fe(η 1-OOCBut)21-HOOCBut)4 containing the high spin iron(II) atom as the major product. Study of the reactions of 3 with a deficiency (<1: 1) and an excess (>1: 1) of diamines demonstrated that the polymer {[(η2-(NH2)2C6H4)2Fe(μ-OOCBut)2][Fe2(μ-OOCBut)4] · · 2MeCN}n is generated as the major product in the former case, whereas the mononuclear complexes Fe(η1-OOCBut)21-(NH2)2C6H4]4 and Fe(η1-OOCBut)22-(NH2)2C6H2Me2][η1-(NH2)2C6H2Me2]2 are predominantly obtained in the latter case. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 779–792, May, 2006.  相似文献   

6.
Two novel bimetallic complexes, [Cr(CO)3(η 6-C6H5)–C≡C–C6H4–Fc] (Fc = C5H5FeC5H4] (1) and [Cr(CO)3(η 6-C6H5)–C ≡ C–Fc–C(CH3)2–Fc] (3), were synthesized by the Sonogashira coupling reaction. By using of (1) and (3) as ligands to react with Co2(CO)8, two others novel polymetallic complexes, [Cr(CO)3(η 6-C6H5){Co2(CO)6-η 2-μ 2-C≡C–}–C6H4–Fc] (2) and [Cr(CO)3(η 6-C6H5){Co2(CO)6-η 2-μ 2-C≡C–}Fc–C(CH3)2–Fc] (4) were obtained. Four carbonyl complexes were characterized by elemental analysis, FT-IR, NMR and MS. The molecular structures of complexes (1), (2) and (4) were determined by single crystal X-ray diffraction. The interactions among the ferrocenyl, Cr(CO)3 and Co2(CO)6-η 2-μ 2-C≡C– units were investigated by cyclic voltammetry.  相似文献   

7.
Summary.  Partial removal of chloride anions from the dimer [Pd(η3-2-CH3*C3H4)(μ-Cl)]2 with AgTf(Tf = CF3SO3) followed by addition of dppm affords [Pd23-Me*C3H4)2(μ-Cl)(μ-dppm)]Tf (1). The substitution of Cl by X (X = pz, SC6F5, S py ) using the appropriate salts yields the new derivatives [Pd23-Me*C3H4)2(μ-X)(μ-dppm)]Tf (24). All complexes exhibit a dinuclear half-A-frame structure with two isomers present in solution. The isomers differ in the relative orientation of the two allyl groups (cis or trans). The isomer interconversion was studied by variable temperature 1H NMR spectroscopy. The molecular structures of 2 and 4 were solved by X-ray diffraction studies. A distorted boat conformation of the seven- or six-membered metallacycle was found in both cases. Received June 7, 2000. Accepted June 20, 2000  相似文献   

8.
The present review is devoted to the chemistry of trimethylacetate NiII complexes with various nitrogen-containing ligands. Pathways of formation of complexes containing the Ni2(μ-OH2)(μ-OOCCMe3)2 and Ni2(μ-OOCCMe3)4 fragments are discussed. Pathways of degradation of the nine-nuclear complex Ni9(HOOCCMe3)44-OH)33-OH)3)34-OOCCMe3)12 under the action of primary amines (aniline or propargylamine) as well as the process of dehydration ofN-phenyl-o-phenylenediamine up to the bischelate mononuclear complex [1,2-(NH)(NPh)C6H4]2Ni are demonstrated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 409–419, March, 1999.  相似文献   

9.
Three diiron carbonyl complexes, namely [(η 5-C5H4)(η 3-C(CH2)2)]Fe2(CO)5 (1), [(C2H5)2C(η 5-C5H4)2]Fe2(μ-CO)2(CO)2 (2), and [(CH2)4C(η 5-C5H4)(η 5-C5H3)(C5H9)]Fe2(μ-CO)2(CO)2 (3), have been synthesized by the reactions of C5H4C(Me)2, C5H4C(Et)2, and C5H4C(CH2)4, respectively, with Fe(CO)5 in refluxing xylene. The complexes have been characterized by elemental analysis, IR, and 1H NMR spectra. The molecular structures of the complexes have been determined by single-crystal X-ray diffraction. The structures of the complexes indicate that fulvenes can be bound to transition metal centers by diverse modes.  相似文献   

10.
The reaction of 2-hydroxy-6-methylpyridine (HL, 1) with nonanuclear nickel trimethyl-acetate Ni9(OH)6(OOCCMe3)12(HOOCCMe3)4 (2) in MeCN with a ratio M: L = 1: 1 under mild conditions (20 °C, 15 min) led to degradation of the metal core to form the hexanuclear complex (HL)22-HL)2Ni63-OH)22-H2O)2(μ-OOCCMe3)8(η-OOCCMe3)2 (3). Further heating of 3 in acetonitrile at 80 °C for 4 h afforded the (HL)Ni63-OH)(μ32-L)3(μ,η2-L)(μ3-L)(μ 3-OOCCMe3)(μ-OOCCMe3)42-OOCCMe3) complex. The reaction with the use of a 2: 1 THF-EtOH mixture instead of acetonitrile at 50 °C gave the decanuclear complex [Ni103-O)23-OH)4(μ-OOCCMe3)632-L)6(EtOH)6](H2O)2, which is also produced from compounds 1 and 2 in ethanol. The structures of the resulting complexes were established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 908–917, May, 2007.  相似文献   

11.
The reactions of polynuclear cobalt(ii) trimethylacetates [Co(OH) n (OOCCMe3)2–n ] x , Co6(3-OH)2(OOCCMe3)10(HOOCCMe3)4, or Co4(3-OH)2(OOCCMe3)6(HOEt)6 with an excess of N-phenyl-o-phenylenediamine (1) in toluene followed by treatment with atmospheric oxygen afforded the diamagnetic complex [Co{2-(NPh)(NH)C6H4}2{1-(NH2)C6H4(NPhH)}]+(Me3CCOO...H...OOCCMe3) (3), whose cation contains the CoIII atom. The reaction of Co4(3-OH)2(OOCCMe3)6(HOEt)6 with a deficient amount of diamine 1 in acetonitrile under an argon atmosphere gave rise to the antiferromagnetic ionic complex [Co{2-(NPh)(NH)C6H4}2MeCN]+[Co2(2,2-OOCCMe3)(2-OOCCMe3)2(2-OOCCMe3)2]·2MeCN (4), whose cation is an isoelectronic analog of the cation in complex 3. The structures of the new compounds were established by X-ray diffraction analysis.  相似文献   

12.
Eight dinuclear rhodium(II) complexes containing various, (primarily, polyfunctional) N-donor ligands in the trans position with respect to the Rh-Rh bond were synthesized and characterized by X-ray diffraction. In the Chinese-lantern dinuclear rhodium(II) pivalates, RhII 2 (μ-OOCCMe3)4(L)2 (L is 2,3-diaminopyridine (2), 7,8-benzoquinoline (4), 2,2′:6′,2″-terpyridine (5), N-phenyl-o-phenylenediamine (7)), and RhII 2 (μ-OOCCMe3)4L1L2 (3, L1 is 2-phenylpyridine, L2 = MeCN), the steric effects of the axial ligands are most strongly reflected in the Rh-N(L) and Rh-Rh bond lengths. The introduction of chelating ligands containing a conformationally rigid chelate ring leads to the cleavage of two carboxylate bridges to form the dinuclear double-bridged structure RhII 2 (μ- OOCCMe3)2(OCCMe3)22-L3)2, where L3 is 8-amino-2,4-dimethylquinoline (6). The reaction of complex 7 containing coordinated N-phenyl-o-phenylenediamine with pyrrole-2,5-dialdehyde afforded the new RhII 2(μ-OOCCMe3)4(L4)2 complex (8) containing 5-(1-phenyl-1-H-benzimidazol-2-yl)-1H-pyrrole-2-carbaldehyde (L4) in the axial positions of the dirhodium tetracarboxylate fragment. The coordinated diamine differs in reactivity from the free diamine. The reaction of the former with the above dialdehyde affords the [1+1]-condensation product, viz., 5-{(E)-[(2-anilinophenyl)imino]methyl}-1-H-pyrrole-2-carbaldehyde, whereas the reaction of unsubstituted o-phenylenediamine gives 5-{(E)-[(2-aminophenyl)imino]methyl}-1-H-pyrrole-2-carbaldehyde (L5) . The reaction of the latter with RhII 2(μ-OOCCMe3)4(H2O)2 affords the dinuclear complex RhII 2(μ-OOCCMe3)2(OOCCMe3)22-L5)2 (9), which is an analog of complex 6 containing only two bridging carboxylate groups.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 581–591, March, 2005.  相似文献   

13.
The static magnetic susceptibility of mononuclear trimethylacetate nickel complex Ni(NH2Ph)4(OOCCMe3)2 (3) and binuclear complexes Ni2(μ-OH2)(μ-OOCCMe3)2(OOCCMe3)2(dipy)2 (4) and Ni2(μ-OOCCMe3)4py2 (5) was measured in the temperature range of 2–300 K. The magnetic behavior of3 is typical of mononuclear complexes with the Ni11 atom in the octahedral environment. Numerical calculations of the temperature dependence of magnetic susceptibility with inclusion of isotropic exchange interactions (J) and single-ion initial splitting parameters showed that the magnetic behavior of complexes4 and 5 can be interpreted in terms of ferromagnetic (for4) and antiferromagnetic (for5) interactions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 437–442, March, 2000.  相似文献   

14.
The reaction of 2-hydroxy-6-methylpyridine with Co(NO3)2·6H2O or Co(F3CSO3)2·6H2O in the absence of a deprotonating agent produces the mononuclear complexes Co(HL)4(NO3)2 or Co(HL)4(F3CSO3)2 (HL is 6-methyl-2-pyridone), respectively. In the presence of triethylamine, the reaction affords the trinuclear complex Co3(HL)2(L)4(NO3)2 or the heptanuclear dicationic complex [Co7L12]·(F3CSO3)2·4MeCN in the case of cobalt nitrate or cobalt trifluoromethanesulfonate, respectively. When HL is deficient, the replacement of the trimethylacetate anions in polymeric cobalt pivalate [Co(OH)n(OOCCMe3)2−n ]x gives rise to the hexanuclear complex Co63-OH)223-L)2(μ-OOCCMe3)8(HOOCCMe3)4, whereas the HLCo63-OH)(η23-L)32,μ-L) (μ3-L)(μ3-OOCCMe3)(μ-OOCCMe3)42-OOCCMe3) complex is generated when HL is present in excess. The structures of the reaction products were established by X-ray diffraction. Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1851–1862, November, 2006.  相似文献   

15.
The reactions of ytterbium naphthalene complex C10H8Yb(THF)2 with 2-cyclopentadienylethanol, 1-cyclopentadienylpropan-2-ol, 3-cyclopentadienyl-1-butoxypropan-2-ol, and cyclopentadienyldimethylsilyl-tert-butylamine were studied. The bivalent ytterbium complexes with chelate bifunctional cyclopentadienyl ligands [(η5−C5H5)CH2CH21−O)]Yb(THF), [(η5−C5H5)CH2CH21−O)]Yb(DME). [(η5−C5H5)CH2CH(Me)(η1−O)]Yb(THF), [(η5−C5H5)CH2CH(CH2OC4H9)(η1−O)]Yb(THF), and [(η5−C5H5)SiMe21−N(Bu1))]Yb(THF) were obtained and characterized. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 742–745, April, 2000.  相似文献   

16.
Interaction of ortho-phenylenediamine with the nonanuclear nickel trimethylacetate cluster Ni9(4-OH)3(3-OH)3( n -OOCMe3)12(HOOCCMe3)4(I) in an amine deficiency yields the antiferromagnetic trinuclear complex [Ni3{-N,N"-(NH2)2C6H4}2(HCCOOCMe3)3(3-OH)(-OOCCMe3)4]+(OOCCMe3)(III) containing bridging diamine ligands. Reaction of excess diamine with Ior IIIleads to the formation of the paramagnetic monomer Ni{2-o-(NH2)2C6H4}2(OOCCMe3)2(IV), which reacts with atmospheric oxygen to form the known bis(semiquinonediimine) complex Ni[1,2-(NH)2C6H4]2(V).  相似文献   

17.
The difurylphosphido-bridged dinuclear complex [Ru2(CO)6(μ-PFu2)(μ-η12-Fu)] (Fu = 2-furyl) 1 readily reacts with two equivalents of each of the terminal alkynes HC≡CR (R = Fc, p-C6H4Fc, p-C6H4NO2, Fc = Fe(η5-C5H5)(η5-C5H4)) by an interesting head-to-tail ynyl coupling with a furan group to form a series of phosphido-bridged diruthenium compounds containing a novel furyl-substituted C4 hydrocarbyl chain of stoichiometry [Ru2(CO)4(μ-PFu2){μ-η1123-RCC(H)C(R)C(H)Fu}] (R = Fc 2, p-C6H4Fc 3, p-C6H4NO2 4) in moderate to good yields. Reaction of 1 with an equimolar amount of HC≡CFc and HC≡C(p-C6H4NO2) afforded a pair of isomers of [Ru2(CO)4(μ-PFu2){μ-η1123-R1CC(H)C(R2)C(H)Fu}] (R1 = Fc, R2 = p-C6H4NO2 5a; R1 = p-C6H4NO2, R2 = Fc 5b) together with a small mixture of 4. X-ray crystal structures of 2, 3, 5a and 5b are reported. All of these new alkyne-derived dinuclear complexes are electron precise with 34 cluster valence electrons in which the μ-η12-furyl ligand acts as a three-electron donor and the μ-phosphido Ru2 framework is retained in the products upon alkyne coupling reactions. The resulting organic fragment of each complex is coordinated to the Ru atoms via a π, a π-allyl and two σ bonds, and donates seven electrons to the metal core. Dedicated to the memory of Professor F. Albert Cotton.  相似文献   

18.
The solid-state thermal decomposition of the dinuclear pivalate complexes LM(μ-OOCR)4ML, both those synthesized earlier (M = MnII, FeII, or CoII; L = 2,6-(NH2)2C5H3N)) and new complexes (M = CuII; L = 2,6-(NH2)2C5H3N or (2-NH2)(6-CH3)C5H3N), was studied by differential scanning calorimetry and thermogravimetry. The decomposition of the CoII complexes is accompanied by the aggregation to form the volatile octanuclear complex Co84-O)2n-OOCCMe3)12 (n = 2 or 3), whereas the thermolysis of the MnII, FeII, and CuII complexes is destructive, the phase composition of the decomposition products being substantially dependent on the nature of metal and the α substituent R in the apical organic ligand.  相似文献   

19.
Transformations of polymeric trimethylacetate complexes [M(OH) n (OOCCMe3)2 – n ] m (M = Ni (I) and Co (II)) and clusters Ni9(4-OH)3(3-OH)3(-O,O-OOCCMe3)(-O,O"-OOCCMe3)7(3-O,O,O"-OOCCMe3)3(4-O,O,O",O"-OOCCMe3)(HOOCCMe3)4(III) and Co6(3-OH)2(-OOCCMe3)10(HOOCCMe3)4(VIII), which are formed from Iand IIupon their recrystallization from nonpolar solvents, were studied. It was shown that the action of N-phenyl-o-phenylenediamine (L) on Ior IIIresults, depending on the solvent, in different tetranuclear clusters with the hydroxo bridges. For example, in benzene, the L2Ni4(3-OH)2(HOOCCMe3)4(-OOCCMe3)6complex (IX) is formed; its L molecules are coordinated in a monodentate way, whereas in acetonitrile, they chelate to give the {[o-C6H4(NH2)(NHPh)]2Ni4(3-OH)2(MeCN)2(OOCCMe3)2(-OOCCMe3)4} compound (X). Heating of Xin the presence of atmospheric oxygen yields IX, the mononuclear bissemiquinonediimine [o-C6H4(NH)(NPh)]2Ni complex (XI), and water. It was noted that the use of aniline in these reactions affords, independent of the nature of the solvent, only one (NH2C6H5)2Ni4(3-OH)2(HOOCCMe3)4(-OOCCMe3)6cluster (VI); in acetonitrile, this cluster is formed as the solvate VI· 2HOOCCMe3(VIa). When treated with ethanol, Iand IIIgive the Ni4(EtOH)6(3-OH)2(2-OOCCMe3)4(OOCCMe3)2cluster (V), which is structurally close to the known cobalt-containing analog IV. Thermolysis of IVin decalin at 170° causes its dimerization, giving the octanuclear Co8(4-O)2( n -OOCCMe3)12complex (VII) with the tetradentate oxo bridges.  相似文献   

20.
The reactions of the polymeric complex [Co(OH)n(OOCCMe3)2–n ]x (1) with 2-amino-5-methylpyridine (L1) and 2,6-diaminopyridine (L2) under anaerobic conditions at the ratio M : L = 1 : 1 afforded the binuclear complexes Co2(-OOCCMe3)4[-MeC5H3N(NH2)]2 (2) and Co2(-OOCCMe3)4[-C5H3N(NH2)2]2 (3), respectively, with Chinese-lantern-like structures. The reaction of the tetranuclear cobalt(ii) complex Co4(3-OH)2(-OOCCMe3)4(2-OOCCMe3)2(EtOH)6 (4) with 2,6-diaminopyridine under anaerobic conditions at the ratio M : L2 = 2 : 1 gave rise to the antiferromagnetic tetranuclear complex Co4(4-O)[-C5H3N(NH2)2]2(-OOCCMe3)4(2-OOCCMe3)2 (5) with tetradentate-bridging coordination of the oxygen atom. The structures of the compounds synthesized were established by X-ray diffraction analysis.  相似文献   

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