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1.
The synthesis of a new, paramagnetic closo-[(8-(-CH 2CH 2O) 2-1,2-C 2B 9H 10)(1′,2′-C 2B 9H 11)-3,3′-Fe] 0 ( 3) is reported. This compound can serve as a versatile building block for construction of both anionic and zwitterionic derivatives, as exemplified by the synthesis of a series of compounds of general formula closo-[(8-X-(CH 2CH 2O) 2-1,2-C 2B 9H 10)(1′,2′-C 2B 9H 11)-3,3′-Fe], bearing organic end groups (X = NC 5H 5 ( 4), (C 6H 5) 3P ( 5), OH ( 6), and 2-O(1-CH 3O-C 6H 4) ( 7)) attached to the cluster by a diethyleneglycol spacer. Molecular structures of 3, 4, 5 and 7 were determined by single-crystal X-ray diffraction analysis and by the long-time neglected method of paramagnetic, high field NMR ( 1H, 13C and 11B) spectroscopy. 相似文献
2.
Dioxomolybdenum(VI) complexes [MoO 2(B 1)H 2O] ( 1), [MoO 2(B 2)EtOH] ( 2), [MoO 2(B 3)EtOH] ( 3) and [MoO 2(B 4)EtOH] ( 4) were synthesized using the Schiff base ligands H 2B 1(previously reported), H 2B 2, H 2B 3 and H 2B 4, respectively. These ligands were prepared by condensation of 1-(2-pyridyl) 5-methyl 3-pyrazole carbohydrazide with salicylaldehyde, o-hydroxy acetophenone, 5-bromo salicylaldehyde and 5-nitro salicylaldehyde respectively. Due to the presence of a substituted 1-(2-pyridyl) pyrazole unit, ligands H 2B 1, H 2B 2 and H 2B 3 exhibit fluorescent emissions, and the most intense emission was obtained for H 2B 3. H 2B 4 is incapable of showing fluorescence emission. As the ligands are capable of using different binding modes, according to the demands of the guest metal ions, their emission properties also change accordingly. The dioxomolybdenum(VI) complex of the ligand H 2B 1, i.e. complex 1, shows quenched emission compared to H 2B 1. Again when Cu 2+, Co 2+ or Ni 2+ ions are added to a solution of 1, in each case a new complex of Cu 2+ Co 2+ or Ni 2+ is formed in solution and further quenching was observed. However, with Zn 2+ input to a solution of 1, fluorescence recovery was observed up to the level of the free ligand. The copper(II) complex of H 2B 1 (complex 5), produced by adding equivalent amount of Cu 2+ salt to a solution of 1, was isolated and characterized. One of the dioxomolybdenum(VI) complexes, 3, when subjected to an oxo-transfer reaction with PPh 3 produces complex [MoO(B 3)CH 3CN] ( 6). Complex 6 shows reduced fluorescence emissions compared to 3 in the solid phase. These observations open up the possibilities for these ligands to work as fluorescent signaling system with different metal ion inputs. All the complexes are characterized by elemental analyses, electronic spectra, IR, 1H NMR, magnetic measurements, EPR and by cyclic voltammetry. Complexes 1 and 5, as well as the ligands H 2B 2 and H 2B 3, have been crystallographically characterized. 相似文献
3.
Halogenation of 9-dimethylsulfonium-7,8-dicarba- nido-undecaborane [9-SMe 2-7,8-C 2B 9H 11] with N-chlorosuccinimide, bromine and iodine gave the expected corresponding halogen derivatives [9-SMe 2-11-X-7,8-C 2B 9H 10], where X = Cl ( 1), Br ( 2), I ( 3). In the bromination reaction, [9-SMe 2-6-Br-7,8-C 2B 9H 10] ( 4) was isolated as a minor product being the first example of substitution at a “lower” belt of the 7,8-dicarba- nido-undecaborate cage. The use of excess of bromine resulted in dibromo derivative [9-SMe 2-6,11-Br 2-7,8-C 2B 9H 9] ( 5). Structures of the compounds prepared were determined using 11B- 11B COSY NMR spectroscopy (for all halogen derivatives) and single crystal X-ray diffraction (for compounds 2, 3, and 5). 相似文献
4.
Cluster opening of [2-Cp-9- tBuNH- closo-2,1,7,9-FeC 3B 8H 10] ( 1) , followed by oxidation, generates complexes [2-Cp-8- tBuNH- closo-2,1,8,10-FeC 3B 8H 10] ( 2), [2-Cp-4- tBuNH- closo-2,1,4,12-FeC 3B 8H 10] ( 3), [2-Cp-1- tBuNH- closo-2,1,7,10-FeC 3B 8H 10] ( 4), and [1-Cp-10- tBuNH- closo-1,2,3,10-FeC 3B 7H 9] ( 5). Another variation of the syntheses led to compounds [2-Cp- closo-2,1,8,10-FeC 3B 8H 11] ( 6), [4-Cp-1- tBuNH- closo-4,1,6,8,-FeC 3B 9H 11] ( 7) and to two isomeric, not yet fully characterized, 13-vertex compounds of general nido structure [ tBuNH-Cp-FeC 3B 9H 12] ( 8 and 9). 相似文献
5.
Synthesis procedures for coordination compounds of iron(II) 1,5,6,10-tetra(R)-7,8-dicarba- nido-undecaborates(-1) (carboranes) with tris(pyrazol-1-yl)methane (HC(pz) 3) of the composition [Fe{HC(pz) 3} 2]A 2· nH 2O (A = (7,8-C 2B 9H 12) ? ( I), (1,5,6,10-Br 4-7,8-C 2B 9H 8) ? ( II), (1,5,6,10-I 4-7,8-C 2B 9H 8) ? ( III), n = 0–2) are developed. The compounds are studied by static magnetic susceptibility in the temperature range of 160–500 K, electron (diffuse reflectance spectra), IR, and Mössbauer spectroscopy methods. It is shown that the complexes have high-temperature spin-crossover 1 A 1 ? 5 T 2. Transition temperatures ( T c) for I–III are 370 K, 380 K, and 400 K respectively. Spin-crossover is accompanied by thermochromism (color change: pink ? white). 相似文献
6.
The oxidation of 1,2-C2B10H12 (1) with 100% nitric acid was studied in two solvents (CH2C12 and CCl4). Under the action of superacid (CF3SO3H), the compound 9-HO-1,2-C2B10H11 (2) gives the onium cation 9-H2O+-1,2-C2B10H11 involved in the salt [9-H2O+-1,2-C2B10Hn]-CF3SO3?, as demonstrated by uB NMR spectroscopy. The experimental and simulated uB NMR spectra of the cation 9-H2O+-1,2-C2B10H11 are in satisfactory agreement with each other. In the presence of a base, compound 2 is transferred from an ethereal solution to an aqueous alkaline solution giving the anion 9-O?- 1,2-C2B10H11. The structure of compound 2 was confirmed by 1H, 11B, 11B1H, 11B-11B COSY NMR spectroscopy, IR spectroscopy, and gas chromatography mass spectrometry and was additionally established by X-ray diffraction. 相似文献
7.
We report two methods for preparing N-arylammonio, N-pyridyl and N-arylamino dodecaborates: heating of the tetrabutylammonium salt of dodecahydro- closo-dodecaborate(2-) with aryl and pyridyl amines, or nucleophilic attack of [ closo-B 12H 11NH 2] 2− on a strongly deactivated aromatic system. With aryl amines we obtained [1- closo-B 12H 11N(R 1) 2C 6H 5] − (R 1 = H, CH 3). With 4-(dimethylamino)pyridine, [1- closo-(B 12H 11NC 5H 4)-4-N(CH 3) 2] −, with a bond between the boron and the pyridinium nitrogen, was obtained. A presumable mechanism for this kind of reactions is reported. By nucleophilic substitution, two products, [1- closo-(B 12H 11NHC 6H 3)-3,4-(CN) 2] 2− and [1- closo-(B 12H 11NHC 6H 2)-2-(NO 2)-4,5-(CN) 2] 2−, were formed with 4-nitrophthalonitrile and 1-chloro-2,4-dinitrobenzene gave [1- closo-(B 12H 11NHC 6H 3)-2,4-(NO 2) 2] 2−. For [1- closo-B 12H 11N(CH 3) 2C 6H 5] − and [1- closo-(B 12H 11NHC 6H 3)-2,4-(NO 2) 2] 2− single crystal X-ray structures were obtained. 相似文献
8.
The reaction of Li[ closo-1-Me-1,2-C 2B 10H 10] with cyclohexene oxide produced closo-1-Me-2-(2′-hydroxycyclohexyl)-1,2-C 2B 10H 10 ( 1) in 86% yield. Decapitation of ( 1) with potassium hydroxide in refluxing ethanol gave the corresponding cage-opened potassium salt of the carborane anion, [ nido-1-Me-2-(2′-hydroxycyclohexyl)-1,2-C 2B 9H 10] − ( 2) in 82% yield. Deprotonation of ( 2) with two equivalents of n-butyllithium in THF at −78 °C, followed by its further reaction with anhydrous MCl 4 · 2THF (M = Ti, Zr) produced the corresponding d0-half-sandwich metallacarboranes, closo-1-M(Cl)-2-Me-3-(2′-σ- O-cyclohexyl)-η 5-2,3-C 2B 9H 9 ( 3 M = Zr; 4 M = Ti), in 59% and 51% yields, respectively. Reaction of Li[ closo-1,2-C 2B 10H 11] with Merrifield’s peptide resin (1%) in refluxing THF gave the ortho-carborane-functionalized polymer ( 5) in 88% yield. The corresponding closo-1-polystyryl-2-(2′-hydroxycyclohexyl)-1,2-C 2B 10H 10 ( 6) was produced in 94% yield by refluxing a mixture of the lithium salt of ( 5) and cyclohexene oxide in THF for 2 days. Compound ( 6) was decapitated, deprotonated and then reacted with ZrCl 4 · 2THF to produce a polymer-supported d0-half-sandwich metallacarborane closo-1-Zr(Cl)-2-polystyryl-3-(2′-σ- O-cyclohexyl)-η 5-2,3-C 2B 9H 9 ( 7) in 41% yield. Compounds ( 3) and ( 7), in the presence of MMAO-7 (13% ISOPAR-E), were found to catalyze the polymerization of ethylene and vinyl chloride in toluene to give high molecular weight PE (9.4 × 10 3 ( Mw/ Mn = 1.8)) and PVC (2.1 × 10 3 ( Mw/ Mn = 1.6)), respectively. 相似文献
9.
New radical cation salts (BEDT-TTF) 2[3,3′-Co(1,2-C 2B 9H 11) 2] ( 1), (BEDT-TTF) 2[8- I-3,3′-Co(1,2-C 2B 9H 10)(1′,2′-C 2B 9H 11)] ( 2), (BMDT-TTF)[3,3′-Co(1,2-C 2B 9H 11) 2] ( 3) and (TMTSF) 2[3,3′-Fe(1,2-C 2B 9H 11) 2] ( 4) were synthesized and their crystal structures and electrical conductivities were determined. Compound 4 is isostructural to the earlier reported Co analogue. All the radical cation salts synthesized are semiconductors. 相似文献
10.
The 8,9′-[ closo-{3-Co(η 5-C 5H 5)-1,2-C 2B 9H 10}] 2 ( 1) species, in which two large closo-CoC 2B 9 sub-clusters are connected by a B-B bond, is unexpectedly obtained from the reaction of closo-[3-Co(η 5-C 5H 5)-1,2-C 2B 9H 11] with sulfur in the presence of aluminium chloride under reflux conditions. The solid state conformation of 1 seems to be the result of a pair of intramolecular C-H?H-B dihydrogen bonds between the protonic H atoms of the C 5H 5 fragment of a sub-cluster and the hydridic H atoms of the C 2B 9H 11 fragment in the other sub-cluster in 1. 相似文献
11.
The reaction of gaseous HCl with either the disodium or dilithium compound of the [ nido-2,4-(SiMe 3) 2-2,4-C 2B 4H 4] 2− dianion ( I) in 1:1 stoichiometry in THF produced the monoprotonated species 1-Na(THF) 2-2,4-(SiMe 3) 2-2,4-C 2B 4H 5 ( II) or 1-Li(THF) 2-2,4-(SiMe 3) 2-2,4-C 2B 4H 5 ( III), in 81% and 80% yields, respectively. This method proved superior to that involving the direct reduction of the closo-C 2B 4 carborane by metal hydrides. II and III were characterized by elemental analysis, 1H, 11B and 13C NMR and IR spectra. Compound II was recrystallized from a mixture THF, hexane and TMEDA (1:2:1) to isolate colorless crystals of the mixed solvated species, 1-(THF)-1-(TMEDA)-1-Na-2,4-(SiMe 3) 2-2,4-C 2B 4H 5 ( IV), which were subsequently used for X-ray diffraction studies. The structure of IV showed that the capping metal occupied the apical position above the open C 2B 3 face of the carborane and that a hydrogen atom was bridging the two adjacent boron atoms on that face. The 11B and 13C NMR spectra calculated by GIAO (gauge independent atomic orbital) methods at the 6-311G ** level on the B3LYP/6-31G * optimized geometries of I– III, and a number of related nido- and closo-carboranes, gave excellent agreement with experiment, even in compounds where electron correlation effects are known to be important. 相似文献
12.
A series of chain multinuclear cobaltacarboranes of the general formula [(C 2B 9H 11) 2Co n (C 2B 8H 10) n?1] n?, where n = 4 to 7, were synthesized. These compounds, containing derivatives of ortho-carborane(12) as ligands and dicarbollide C 2B 9H 1 2? and bidentate dicarbacanastide C 2B 8H 11 4? ligands, were studied by IR, UV, and H and 11B NMR spectroscopy. The nonequivalence of the dicarbacanastide ligands that occupy different positions in the chain with respect to the terminal dicarbollide ligands was discovered. 相似文献
13.
Complex Cp∗PtCl 2 (Cp∗ = η-C 4Me 4) reacts with the carborane anions [7,8-C 2B 9H 11] 2− and [9-SMe 2-7,8-C 2B 9H 10] − giving platinacarboranes Cp∗Pt(η-7,8-C 2B 9H 11) ( 1) and [Cp∗Pt(η-9-SMe 2-7,8-C 2B 9H 10)] + ( 2), respectively. Reactions of the [Cp∗Pt] 2+ fragment (as a labile nitromethane solvate) with the sandwich compounds Cp∗Fe(η-C 5H 3Me 2BMe) and Cp∗Rh(η 5-C 4H 4BPh) afford the triple-decker cations [Cp∗Pt(μ-η:η-C 5H 3Me 2BMe)FeCp∗] 2+ ( 3) and [Cp∗Pt(μ-η 5:η 5-C 4H 4BPh)RhCp∗] 2+ ( 4) with bridging boratabenzene and borole ligands. The structures of 1 and 3(CF 3SO 3) 2 were determined by X-ray diffraction. 相似文献
14.
A reaction of complexes CoCl 2(dppe) (dppe is the 1,2-bis(diphenylphosphino)ethane) or CoCl 2(dppp) (dppp is the 1,3-bis(diphenylphosphino)propane) with [K][7,8- nido-C 2B 9H 12] upon reflux in benzene led to the mixed ligand closo-cobaltacarboranes [3,3-(Ph 2P(CH 2) n PPh 2)-3-Cl- closo-3,1,2-Co IIIC 2B 9H 11] ( n = 2 and 3, respectively) in moderate yields (34 and 16%). The structure of the 18-electron complexes in solution and the solid state was studied by NMR and IR spectroscopy, the structure in the case of the closo-complex with dppe-ligand was confirmed by X-ray crystallography. 相似文献
15.
Addition of ethynylferrocene to nido-1,2-(Cp ∗RuH) 2B 3H 7 ( 1) at ambient temperature leads to nido-1,2-(Cp ∗Ru) 2(1,5-μ-C{Fc}Me)B 3H 7 ( 2, 3) and closo-4-Fc-1,2-(Cp ∗RuH) 2-4,6-C 2B 2H 3 ( 4). Compounds 2 and 3 represent a pair of geometric isomers, nido-species in which the regiochemistry of the alkyne reduction conforms to the Markovnikoff rule. Compound 4 is an octahedral structure in which the inserted alkyne is on an open face of the closo cluster. 相似文献
16.
An ab initio molecular orbital study shows that the face hydrogen of the zwitterionic hemiousene [7.11 1]- nido-(12)-7,8-dicarbahemiousene (C 7H 6+-B 9C 2H 11−) is in a fluxional double minimum. It is primarily associated with B10 and forms unsymmetrical three-center bridges between B10-B9 or B10-B11. The transition barrier is about 2.5 kcal mol −1. This structure is similar to that of the unsubstituted C 2B 9H 12− ion and demonstrates that the cationic tropyliumyl substituent has little effect on the face. The hypothetical completely symmetrical ion B 11H 123− does not have a centered face hydrogen. The hydrogen is involved in a short, symmetrical bridge between face borons, and would be presumably fully fluxional in solution. 相似文献
17.
Synthesis and Crystal Structures of [P(C 6H 5) 4][1-(NH 3)B 10H 9] and Cs[(NH 3)B 12H 11] · 2CH 3OH The reduction of [1-(NO 2)B 10H 9] 2? with aluminum in alkaline solution yields [1-(NH 3)B 10H 9] ? and by treatment of [B 12H 12] 2? with hydroxylamine-O-sulfonic acid [(NH 3)B 12H 11] ? is formed. The crystal structures of [P(C 6H 5) 4][1-(NH 3)B 10H 9] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH 3)B 12H 11] · 2CH 3OH (monoclinic, space group P2 1/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion. 相似文献
18.
The treatment of 1,2-, 1,7- and 1,12-carbaborane lithiated isomers with [3,3′-Co-8-(CH 2CH 2O) 2-(1,2-C 2B 9H 10)-(1′,2′-C 2B 9H 11)] ( 1) at molar ratios 1:1 or 1:2 at room temperature in THF leads generally to the formation of a series of orange double-cluster mono and dianions. These were characterized by NMR and MS methods as [1′′-X-1′′,2′′- closo-C 2B 10H 11] −, [ 2] −; [1′′-X-1′′,7′′- closo-C 2B 10H 11] −, [ 3] − and [1′′-X-1′′,12′′- closo-C 2B 10H 11], [ 4] − for the monoanions, whereas [1′′,2′′-X 2-1′′,2′′- closo-C 2B 10H 10] 2−, [ 2] 2−; [1′′,7′′-X 2-1′′,7′′- closo-C 2B 10H 10] 2−, [ 3] 2−; and [1′′,12′′-X 2-1′′,12′′- closo-C 2B 10H 10] 2−, [ 4] 2− for the dianions (where X = 3,3′-Co-8-(CH 2CH 2O) 2-(1,2-C 2B 9H 10)-1′,2′-(C 2B 9H 11)). Moreover, these borane-cage subunits can be easily modified via attaching variable substituents onto cage carbon and boron vertices, which makes these compounds structurally flexible potential candidates for BNCT of cancer and HIV-PR inhibition. 相似文献
19.
Preparation, 11B NMR, Vibrational Spectra, and Crystal Structure of [(C 5H 5N) 2CH 2][1-(O 2N)B 10H 9] By reaction of [B 10H 10] 2? in aqueous acetonitrile with a saturated solution of NO 2 in dichloromethane [1-(O 2N) · B 10H 9] 2? and [B 10H 9(NO)B 10H 9] 3? are formed which can be separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound. The X-ray structure determination of [(C 5H 5N) 2CH 2][1-(O 2N)B 10H 9] (triclinic, space group P1 , a = 7.1530(9), b = 8.3753(8), c = 15.198(2) Å, α = 96.00(1), β = 95.48(1), γ = 95.60(1)°, Z = 2) reveals the coordination of the NO 2 group via N with a B1? N distance of 1.535(5) Å and an O2? N? O1 angle of 119.3(3)°. The 11B NMR spectrum exhibits the characteristic feature (1 : 1 : 4 : 4) of an apical monosubstituted B 10 cluster with a strong downfield shift of the ipso-B atom at +13.4 ppm. The IR and Raman spectra show strong NO stretching vibrations at 1381 und 1420 cm ?1. 相似文献
20.
The heterometallic cluster complexes {( p-Cymene)Ru[S 2C 2(B 10H 10)]}Mo(CO) 2{(CO) 3Ru[S 2C 2(B 10H 10)]} ( 2) and {( p-Cymene)Ru[Se 2C 2(B 10H 10)]} 2Mo(CO) 2 ( 3) ( p-Cymene = η 6-4-isopropyl-toluene) have been synthesized from the reactions of 16-electron half-sandwich ruthenium 1,2-dichalcogenolate carborane complexes ( p-Cymene)Ru[E 2C 2(B 10H 10)] (E = S( 1a), Se( 1b)) with Mo(CO) 3(Py) 3 in the presence of BF 3 · Et 2O. The complexes of 2 and 3 were characterized by elemental analysis and IR, NMR spectra. The molecular structure of 2 has been characterized by single-crystal X-ray diffraction analysis. Complex 2 is unsymmetrical and the two Ru–Mo single bonds (2.7893(14), 2.8189(13) Å) are each supported by a symmetrically bridging o-carborane-1,2-dithiolato ligand. 相似文献
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