共查询到20条相似文献,搜索用时 15 毫秒
1.
Xian-Kuan Huo 《Journal of organometallic chemistry》2010,695(17):2007-4263
Two binuclear complexes [Cp∗M(Cl)CarbS]2 (Cp∗ = η5-C5Me5, M = Rh (1a), CarbS = SC2(H)B10H10, Ir (1b)) were synthesized by the reaction of LiCarbS with the dimeric metal complexes [Cp∗MCl(μ-Cl)]2 (M = Rh, Ir). Four mononuclear complexes Cp∗M(Cl)(L)CarbS (L = BunPPh2, M = Rh (2a), Ir (2b); L = PPh3, M = Rh (4a), Ir (4b)) were synthesized by reactions of 1a or 1b with L (L = BunPPh2 (2); PPh3 (4)) in moderate yields, respectively. Complexes 3a, 3b, 5a, 5b were obtained by treatment of 2a, 2b, 4a, 4b with AgPF6 in high yields, respectively. All of these compounds were fully characterized by IR, NMR, and elemental analysis, and the crystal structures of 1a, 1b, 2a, 2b, 4a, 4b were also confirmed by X-ray crystallography. Their structures showed 3a, 3b and 5a, 5b could be expected as good candidates for heterolytic dihydrogen activation. Preliminary experiments on the dihydrogen activation driven by these half-sandwich Rh, Ir complexes were done under mild conditions. 相似文献
2.
Jia-Sheng Zhang 《Journal of organometallic chemistry》2007,692(18):3944-3948
Two hetero-binuclear complexes [Cp∗CoS2C2(B9H10)][Rh(COD)] (2a) and [Cp∗CoSe2C2(B10H10)][Rh(COD)] (2b) [Cp∗ = η5-pentamethylcyclopentadienyl, COD = cyclo-octa-1,5-diene (C8H12)] were synthesized by the reactions of half-sandwich complexes [Cp∗CoE2C2(B10H10)] [E = S (1a), Se (1b)] with low valent transition metal complexes [Rh(COD)(OEt)]2 and [Rh(COD)(OMe)]2. Although the reaction conditions are the same, the structures of two products for dithiolato carborane and diselenolato carborane are different. The cage of the carborane in 2a was opened; However, the carborane cage in 2b was intact. Complexes 2a and 2b have been fully characterized by 1H, 11B NMR and IR spectroscopy, as well as by elemental analyses. The molecular structures of 2a and 2b have been determined by single-crystal X-ray diffraction analyses and strong metal-metal interactions between cobalt and rhodium atoms (2.6260 Å (2a) and 2.7057 Å (2b)) are existent. 相似文献
3.
《Journal of Coordination Chemistry》2012,65(7):1219-1235
Two new heterometallic compounds, [Ni(bpy)3][Mn(NCO)4]·H2O (1) and [Ni(phen)3]2[Zn(NCO)4]2·4DMSO·H2O (2) [bpy?=?2,2′-bipyridine and phen?=?1,10-phenanthroline], have been synthesized and characterized. The structures of 1 and 2 were solved by single-crystal X-ray diffraction analysis. The cationic moieties of [Ni(bpy)3]2+ in 1 and [Ni(phen)3]2+ in 2 show octahedral environments around Ni(II), whereas the anionic groups of [Mn(NCO)4]2? in 1 and [Zn(NCO)4]2? in 2 exhibit tetrahedral geometry around the Mn(II) and Zn(II), respectively. Both compounds are catalysts in the H/D exchange of salicylaldehyde in DMSO-d6 which takes place under mild conditions and short reaction time. 相似文献
4.
The binuclear half-sandwich iridium complexes {Cp∗IrCl2}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (3) and {Cp∗Ir[E2C2(B10H10)]}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (E = S(5a), Se(5b)) were prepared from the reaction of [Cp∗IrCl(μ-Cl)]2 or the “pseudo-aromatic” half-sandwich iridium complex Cp∗Ir[E2C2(B10H10)] (E = S(4a), Se(4b)) with a tetrathiafulvalene (TTF) derivative 2,6-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene (2) at room temperature. The complexes (3, 5a and 5b) have been fully characterized by IR and NMR spectroscopy, as well as elemental analysis. And the molecular structures of 2 and 5a were established through X-ray crystallography. It is interesting that infinite tunnels are created by repeating ‘buckled bowl’ molecules of 5a. 相似文献
5.
Xu-Qiong Xiao 《Journal of organometallic chemistry》2008,693(2):316-320
A new route was used to synthesize half-sandwich rhodium complexes containing both N-heterocyclic carbenes (NHC) and carborane ligands. The rhodium carbene complexes Cp∗Rh(L)[S2C2(B10H10)] (Cp∗ = pentamethylcyclopentadienyl, L = 1,3-dimethylimidazolin-2-ylidene; 4) can be obtained from the reaction of Cp∗Rh(L)Cl2 (2) with Li2S2C2(B10H10) or from the reaction of Cp∗Rh[S2C2(B10H10)] (3) with silver-NHC complex prepared by direct reaction of an imidazolium precursor and Ag2O. Complexes 2 and 4 were characterized by IR, NMR spectroscopy, element analysis and X-ray structure analyses. 相似文献
6.
Michael Schley 《Journal of organometallic chemistry》2009,694(16):2480-2878
Mononuclear and heterodinuclear complexes of the salen-type ligand H2LH2 [H2LH2 = 2,2′-[1,2-dihydroxybenzene-4,5-diylbis(nitrilomethylidine)]bis(3,5-di-tert-butylphenol)] were prepared, whereof [{Mn(CH3OH)2}LH2]Cl, [ML()] (M = Ni, Cu, CrCl(py); py = pyridine, Cp∗ = pentamethylcyclopentadienyl) were characterized by X-ray analysis. Additionally, cyclic voltammetric investigations were performed to ascertain the influence of the second transition metal complex fragment []2+ on the metallo salen ligand. Moreover, the complexes were tested in the catalytic epoxidation of styrene. Although the complexes are quite sensitive towards oxidants, monometallic complex [{Mn(CH3OH)2}LH2]Cl exhibited a conversion of 70.6% with styrene oxide selectivity of 88% over 1 h at room temperature. 相似文献
7.
Xiu-Feng Hou 《Journal of organometallic chemistry》2004,689(13):2228-2235
Sulfur and oxygen functionalized cyclopentandienyl half-sandwich cobalt dicarbonyl complexes [η5-C5H4(CH2)2SCH2CH3]Co(CO)2 (3) and [η5-C5H4(CH2)2OCH3]Co(CO)2 (7) were prepared. Oxidation of 3 or 7 with I2 led to formation of 18-electron complexes [η5-C5H4(CH2)2SCH2CH3]CoI2 (4) and [η5-C5H4(CH2)2OCH3]Co(CO)I2 (8). The reactions of diiodide complex (4) with dilithium 1,2-dicarba-closo-dodecaborane(12)-1,2-dichalcogenolates [(THF)3LiE2C2B10H10Li(THF)]2 [E=S (1a), Se (1b)] afforded 18-electron mononuclear complexes [η5-C5H4(CH2)2SCH2CH3]Co(E2C2B10H10) [E=S (5a), Se (5b)] in which sulfur atoms of side-chain were attached via an intramolecular coordination. Complex 7 reacted with 1a and 1b to give the binuclear complexes {[η5-C5H4(CH2)2OCH3]Co(E2C2B10H10)}2 [E=S (10a), Se (10b)]. The molecular structures of 5a and 10b were determined by X-ray crystallographic analysis. According to the X-ray structure analyses, 10b contains two o-carborane diselenolate bridges, and each Cp′Co fragment is attached to one terminal and two bridging selenolato ligands. The central Co2Se2 four-membered ring is planar, and the direct metal-metal interaction is absent. 相似文献
8.
An N3-type, Ru heteroleptic complex, AK1, having one bipyridyl ligand modified with COOH groups for tethering to TiO2 and a second bipyridyl ligand modified with two lipoic acid units for binding to platinum, was synthesized. The photophysical and spectroelectrochemical properties were studied in solution, on TiO2, in a dye-sensitized solar cell and on a Pt wire electrode. The results showed that AK1 can produce a photocurrent on TiO2. Furthermore, AK1 binds to Pt via the lipoic acid ligand but not via the carboxylic acid group, and can be electrochemically addressed by the Pt via the lipoic acid linkage. 相似文献
9.
Zhanna DobrokhotovaAnna Emelina Aleksei SidorovGrigory Aleksandrov Mikhail Kiskin Pavel KoroteevMikhail Bykov Marat FazylbekovArtem Bogomyakov Vladimir NovotortsevIgor Eremenko 《Polyhedron》2011,30(1):132-141
Lithium-containing heterometallic complexes with cobalt (Li2Co2(Piv)6(2,4-Lut)2 (2, Piv is the pivalate anion) and Li2Co2(O2CCH2But)6(2,4-Lut)2 (3)) and with nickel (Li2Ni2(Piv)6(DME)2 (4) and Li2Ni2(Piv)6(2,2′-bpy)2 (5)) were synthesized. The structures of the complexes were established by X-ray diffraction. The magnetic properties of complexes 2 and 4 were studied. The thermal behavior of compounds 2, 3, and 5 was investigated. It was shown that the compounds under study can be used as molecular precursors for the synthesis of lithium cobaltate and nickelate. 相似文献
10.
研究了锇-锗单键双金属配合物[OsGe(ArTrip)(PPh3)(H) Cl2] (1)的反应性, 其中 ArTrip=C6H3-2-(η6-Trip)-6-Trip, Trip=2, 4,6-iPr3-C6H3。通过与不同试剂反应, 成功合成并表征了 3个新型锇-锗双金属配合物。通过配合物 1与 EtMgBr反应合成了锗原子上氯原子被溴原子取代的产物[OsGe(ArTrip)(PPh3)(H)Br2] (2); 1 与 LiHBEt3反应合成了锗原子上氯原子被乙基取代的产物[OsGe(ArTrip)(PPh3)(H) Et2] (3); 1 与 HBF4 作用合成了加成产物[OsGe(ArTrip)(PPh3)(H)2Cl2]BF4 (4)。配合物 4 不稳定, 在 H2O(nH2O/n4=1)作用下能转化为配合物 1。 相似文献
11.
研究了锇-锗单键双金属配合物[OsGe(ArTrip)(PPh3)(H)Cl2] (1)的反应性,其中ArTrip=C6H3-2-(η6-Trip)-6-Trip,Trip=2,4, 6-iPr3-C6H3。通过与不同试剂反应,成功合成并表征了3个新型锇-锗双金属配合物。通过配合物1与EtMgBr反应合成了锗原子上氯原子被溴原子取代的产物[OsGe(ArTrip)(PPh3)(H)Br2] (2);1与LiHBEt3反应合成了锗原子上氯原子被乙基取代的产物[OsGe(ArTrip)(PPh3)(H)Et2] (3);1与HBF4作用合成了加成产物[OsGe(ArTrip)(PPh3)(H)2Cl2]BF4 (4)。配合物4不稳定,在H2O (nH2O/n4=1)作用下能转化为配合物1。 相似文献
12.
Xu-Qiong Xiao 《Journal of organometallic chemistry》2011,696(2):504-511
AgOTf (OTf = trifluoromethanesulfonate) shows the reactivity differences when it reacts with carborane complexes [MCl2{(PPh2)2(C2B10H10)}] (M = Ni (2), Pd (3)). The reaction of AgOTf with the palladium complex 3 affords [Pd2(μ-OTf)2{(PPh2)2(C2B9H10)}2] (4) in high yields, while corresponding reaction between the nickel complex 2 and AgOTf leads to the formation of binuclear complexes [Ni{(PPh2)2(C2B9H10)}](μ-Cl)2[Ag{(PPh2)2(C2B10H10)}] (5) and [Ag2(μ-Cl)2 {(PPh2)2 (C2B10H10)}2] (6). The carborane cage of complexes 4 and 5 were broken to form nido-carboranes. It is believed the group 10 metals themselves play an important role in opening the closo-carborane skeleton. Directly stirring [(PPh2)2(C2B10H10)] with AgOTf afforded [Ag2(μ-OTf)2{(PPh2)2(C2B10H10)}2] (7), which is also used to react with 2 and 3. The reaction between 2 and 7 gives only 4 in high yields, however, stirring the mixture of 3 and 7 affords [Pd2(μ-Cl)2{(PPh2)2(C2B9H10)}2] (8), [Pd{(PPh2)2(C2B9H10)}2] (9) and 6. All these complexes have been characterized by IR, 1H NMR, 11B NMR and elemental analyses. Complexes 2, 4-9 have also been determined by single-crystal X-ray diffraction analyses. 相似文献
13.
The prototype hetero-binuclear complexes containing metal-metal bonds, {CpRh[E2C2(B10H10)]}[Fe(CO)3] (Cp = Cp* = eta 5-Me5C5, E = S(5a), Se(5b); Cp = Cp = eta 5-1,3-tBu2C5H3, E = S(6a), Se(6b)) and {CpCo[E2C2(B10H10)]}[Fe(CO)3] (Cp = Cp* = eta 5-Me5C5, E = S(7a), Se(7b); Cp = Cp = eta 5-C5H5, E = S(8a), Se(8b)) were obtained from the reactions of 16-electron complexes CpRh[E2C2(B10H10)] (Cp = Cp*, E = S(1a), Se(1b); Cp = Cp, E = S(2a), Se(2b)), CpCo[E2C2(B10H10)] (Cp = Cp*, E = S(3a), Se(3b); Cp = Cp, E = S(4a), Se(4b)) with Fe(CO)5 in the presence of Me3NO. The molecular structures of {Cp*Rh[E2C2(B10H10)]}[Fe(CO)3] (E = S(5a), Se(5b)), {CpRh[S2C2(B10H10)]}[Fe(CO)3] (6a) {Cp*Co[S2C2(B10H10)]}[Fe(CO)3] (7a) and {CpCo[S2C2(B10H10)]}[Fe(CO)3] (8a) have been determined by X-ray crystallography. All these complexes were characterized by elemental analysis and IR and NMR spectra. 相似文献
14.
Ethan P. McMoran Clement Mugenzi Kyle Fournier Mark Draganjac Donavon Tony Kwangkook Jeong 《Journal of Coordination Chemistry》2016,69(3):375-388
Reaction of N-(4-pyridyl)picolinamide (4-ppa), N-(4-pyridyl)nicotinamide (4-pna), N-(4-pyridyl)isonicotinamide (4-pina), and N-(2-pyridyl)isonicotinamide (2-pina) with divalent metal salts led to the formation of six new coordination complexes. The X-ray structure of [Zn(4-ppa)2Cl2] (1) shows a mononuclear structure with interesting intermolecular hydrogen bonding interactions. [Zn(4-pna)(OAc)2]n (2), Cu(4-pna)(OTf)2(DMF)2]n (3), {[Zn(4-pina)(DMF)4](OTf)2}n (4), {[Fe(4-pina)(DMF)4](OTf)2}n (5), and [Cu(2-pina)(OTf)2(DMF)2]n (6) are one-dimensional coordination polymers with conformational differences caused by the coordination donor disposition, which demonstrates the flexibility of the pyridylamide ligands in polymeric structures. Reflectance UV-visible spectra and thermal properties of the coordination polymers are also reported. 相似文献
15.
Hassan Hadadzadeh Ali R. Rezvani Francine Belanger-Gariepy 《Journal of Molecular Structure》2005,740(1-3):165-168
Several new RhIII complexes, [Rh(tpy)(bpy)L](PF6)2 (tpy=2,2′:6′,2″-terpyridine, bpy=2,2′-bipyridine, and L=monoanions of phenylcyanamide(pcyd)), 4-methylphenylcyanamide (4-MePcyd), 2,4-dimethylphenylcyanamide (2,4-Me2pcyd), 4-methoxyphenylcyanamide (4-MeOPcyd), 2-chlorophenylcyanamide (2-Clpcyd) and 2,5-dichlorophenylcyanamide (2,5-Cl2pcyd) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic absorption spectroscopies. ORTEP drawing of [Rh(tpy)(bpy)(2,5-Cl2pcyd)](PF6)2·1/2CH3CN shows three pyridyl rings of the tpy ligand that are nearly coplanar, as are the two rings of bpy. The anionic cyanamide group is coordinated end-on by the nitrile nitrogen to the RhIII. The RhIII–NCN bond is bent, having an angle of 125.4°. This bent bond is largely determined by the σ-bonding interaction of a cyanamide non-bonding electron pair in a sp2 hybrid orbital. 相似文献
16.
Broderick EM Thuy-Boun PS Guo N Vogel CS Sutter J Miller JT Meyer K Diaconescu PL 《Inorganic chemistry》2011,50(7):2870-2877
Two series of Schiff base metal complexes were investigated, where each series was supported by an ancillary ligand incorporating a ferrocene backbone and different N=X functionalities. One ligand is based on an imine, while the other is based on an iminophosphorane group. Cerium(IV), cerium(III), and yttrium(III) alkoxide complexes supported by the two ligands were synthesized. All metal complexes were characterized by cyclic voltammetry. Additionally, NMR, Mo?ssbauer, X-ray absorption near-edge structure (XANES), and absorption spectroscopies were used. The experimental data indicate that iron remains in the +2 oxidation state and that cerium(IV) does not engage in a redox behavior with the ancillary ligand. 相似文献
17.
Qing Lin Guan Xue Gao Jing Liu Wen Juan Wei Yong Heng Xing 《Journal of Coordination Chemistry》2016,69(6):1026-1038
[Cu2(UO2)4(suc)4(pac)4] (1), [(Cu(H2O)2)(4,4′-bipy)2][(UO2)2(H2O)2(Hca)2]·3H2O (2), and [(Cu(H2O)2)(UO2)(bta)]·4H2O (3) were synthesized by the reaction of succinic acid and 3-pyridinecarboxylic acid, citric acid and 4,4′-bipyridine, or 1,2,4,5-benzenetetracarboxylic acid ligands with Cu(NO3)2·3H2O and UO2(CH3COO)2·2H2O. The complexes were characterized by IR and UV–vis spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, and photoluminescence spectroscopy. Photocatalytic activities of the complexes were also investigated. 相似文献
18.
Three tris(salicyladiminato) samarium complexes were synthesized by the reaction of anhydrous SmCl3 with the sodium salts of the Schiff-bases in THF in 3:1 molar ratio. X-ray diffraction studies revealed that the coordination geometry around samarium atom could be best described as a distorted pentagonal bipyramidal for complexes 1 and 2 and as a distorted tricapped trigonal prism for complex 3. It was found that the coordination environment around samarium atom has significant effect on the catalytic activity of homoleptic Schiff-base complexes of lanthanide. The increasing order of the catalytic activity for the ring-opening polymerization of ε-caprolactone, as well as guanylation of aniline with N,N-diisopropylcarbodiimide is 3 < 2 < 1. 相似文献
19.
Reductive coupling of phenylfulvene with amalgamated calcium metal followed by hydrolysis yields CpPhCHCHPhCp (1) in high yield. Refluxing ligand 1 and Fe(CO)5 in xylene produces (PhCHCHPh)-coupled bis(cyclopentadienyl) tetracarbonyl diiron (PhCHCHPh)[(η5-C5H4)Fe(CO)2]2 (2) as a mixture of meso (2-meso) and racemic isomers (2-rac). The pure racemic isomers of the Mo and W analogues (3-rac and 4-rac) have been synthesized by lithiation of ligand 1 and addition of (MeCN)3M(CO)3 (M = Mo, W) followed by oxidation with 2 equiv. of ferrocenium tetrafluoroborate. All the new complexes have been fully characterized. The molecular structures of 1-meso, 2-meso, 2-rac, 3-rac, and 4-rac have been determined by X-ray diffraction analysis. 相似文献
20.
LU Shi-xiang JIN Guo-xin ** HU Ning-hai JIA Heng-qing . Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun P. R. China . College of Chemistry Jinlin University Changchun P. R. China 《高等学校化学研究》2002,18(4)
IntroductionThe chemistry of chalcogen organometalliccomplexs has become one of the most activebranches in modern chemistry[1] .Itnot only showsthe coordinate variability of organometalliccomplexes but also is applied to studying thereaction mechanism of biologic enzyme[2 ] and thecatalysis of dehydrogenation or hydrogenation inindustry[3] .It is known that transition metalcomplexes react with cyclopentadienyl orsubstituted cyclopentadienyl to form halfsandwichcomplexes with different structur… 相似文献