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1.
The reaction between the 11-vertex rhodathiaborane [8,8-(PPh 3) 2- nido-8,7-RhSB 9H 10] ( 1) and 3-pyridylacetonitrile affords the hydrorhodathiaborane [8,8,8-(PPh 3) 2H-9-(3-Py-CH 2CN)- nido-8,7-RhSB 9H 9] ( 2) in good yield. Treatment of this cluster with ethylene leads to the formation of red, [1,1-(PPh 3)( η2-C 2H 4)-3-(3-Py-CH 2CN)- closo-1,2-RhSB 9H 8] ( 3). Both 11-vertex polyhedral boron-based clusters have been characterized by multielement NMR spectroscopy. In addition, ( 3) has been analyzed by single-crystal X-ray diffraction analysis and is only the second ethylene-ligated metalla-heteroborane to be characterized in the solid state. The molecular structure of this cluster is based on an octadecahedron. In the crystal lattice, the individual clusters form layers supported by short edge-to-face π-interactions between the phenyl rings of neighboring molecules. 相似文献
2.
The reaction of [ nido-7-SB 10H 12] with [RhCl(PPh 3) 3] in the presence of N, N, N′ N′-tetramethylnaphthalene-1,8-diamine (tmnd) in CH 2Cl 2 gives twelve-vertex [2,2-(PPh 3) 2-2-H- closo-2,1-RhSB 10H 10] ( 1) and eleven-vertex [8,8-(PPh 3) 2- nido-8,7-RhSB 9H 10] ( 2), as major products, plus the dimeric species [{(PPh 3)- closo-RhSB 10H 10} 2] ( 3) as a minor product. Reaction of 1 with PMe 2Ph in CH 2Cl 2 results in phosphine exchange and hydride substitution, affording the chloro analogue of 1, [2,2-(PMe 2Ph) 2-2-Cl- closo-2,1-RhSB 10H 10] ( 4). By contrast, reaction between [IrCl(PPh 3) 3] and [ nido-7-SB 10H 12] in CH 2Cl 2 with tmnd affords only one product, twelve-vertex [2,2-(PPh 3) 2-2-H- closo-2,1-IrSB 10H 10] ( 5). [RhCl 2(η 5-C 5Me 5)] 2 with [ nido-7-SB 10H 12] under the same conditions gives twelve-vertex [2-(η 5-C 5Me 5)- closo-2,1-RhSB 10H 10] ( 6). All the compounds are characterised by NMR spectroscopy, and by mass spectrometry, and the molecular structure of [2,2-(PMe 2Ph) 2-2-Cl- closo-2,1-RhSB 10H 10] ( 4) was established by single-crystal X-ray diffraction analysis. This last rhodathiaborane 4 is fluxional in solution through a process that involves a reversible partial rotation of the {RhCl(PMe 2Ph) 2} unit above the {SB 4} pentagonal face of the {SB 10H 10} fragment. 相似文献
3.
The treatment of [1,1‐(PR 3) 2‐3‐(Py)‐ closo‐1,2‐RhSB 9H 8] (PR 3=PMe 3 ( 2 ) or PPh 3 and PMe 3 ( 3 ); Py=pyridine) with triflic acid (TfOH) affords [1,3‐μ‐(H)‐1,1‐(PR 3) 2‐3‐(Py)‐1,2‐RhSB 9H 8] + (PR 3=PMe 3 ( 4 ) or PMe 3 and PPh 3 ( 5 )). These products result from the protonation of the 11‐vertex closo‐cages along the Rh(1)? B(3) edge. These unusual cationic rhodathiaboranes are stable in solution and in the solid state and they have been fully characterized by multinuclear NMR spectroscopy. In addition, compound 5 was characterized by single‐crystal X‐ray diffraction. One remarkable feature in these structures is the presence of three {Rh(PPh 3)(PMe 3)}‐to‐{η n‐SB 9H 8(Py)} ( n=4 or 5) conformers in the unit cell, thus giving an uncommon case of conformational isomerism. [1,1‐(PPh 3) 2‐3‐(Py)‐ closo‐1,2‐RhSB 9H 8] ( 1 ), that is, the bis‐PPh 3‐ligated analogue of compounds 2 and 3 , is also protonated by TfOH, but, in marked contrast, the resulting cation, [1,3‐μ‐(H)‐1,1‐(PPh 3) 2‐3‐(Py)‐1,2‐RhSB 9H 8] + ( 6 ), is attacked by a triflate anion with the release of a PPh 3 ligand and the formation of [8,8‐(OTf)(PPh 3)‐9‐(Py)‐ nido‐8,7‐RhSB 9H 9] ( 9 ). The result is an equilibrium that involves cationic species 6 , neutral OTf‐ligated compound 9 , and [HPPh 3] +, which is formed upon protonation of the released PPh 3 ligand. The resulting ionic system reacts readily with H 2 to give cationic species [8,8,8‐(H)(PPh 3) 2‐9‐(Py)‐ nido‐8,7‐RhSB 9H 9] + ( 7 ). This reactivity is markedly higher than that previously found for compound 1 and it introduces a new example of proton‐assisted H 2 activation that occurs on a polyhedral boron‐containing compound. 相似文献
4.
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
5.
[7,7-(PMe 2Ph) 2-9-( η6- isoPrC 6H 4Me)-7,9-PtRuB 9H 11] has a formal closo Wadian cluster-electron count, but a nido geometry, whereas [1-( η6- isoPrC 6H 4Me)-4,4-(PMe 2Ph) 2-1-4-RuPtB 9H 9], which does have a closo geometry, has a formal sub- closo cluster electron count; both compounds are formed in the reaction between [6-( η6- isoPrC 6H 4Me)- nido-6 RuB 9H 13], KH and [PtCl 2(PMe 2Ph) 2]. 相似文献
6.
[PtCl 2(PPh 3) 2]与B 10H 102-在异丙醇中回流反应, 得到3个巢式十一顶铂十硼烷簇合物: [(PPh 3) 2PtB 10H 11-9- O- i-Pr] ( 1), [(PPh 3) 2PtB 10H 10-8,10-( O- i-Pr) 2] ( 2)和[(PPh 3) 2PtB 10H 11-8- O- i-Pr] ( 3). 簇合物 1~ 3都具有PtB 10多面体骨架结构, 其中Pt原子位于敞开的PtB 4面上, 且与4个B原子成键, 每个Pt原子还与2个PPh 3基团中的P原子成键. 将溶剂热合成的方法引入到硼簇合物的合成中并进行同一反应, 得到2个B 10H 102-降解的巢式十一顶双铂九硼烷簇合物: [(PPh 3) 2(μ-PPh 2)Pt 2B 9H 6-3,9,11-( O- i-Pr) 3] ( 4)和[(PPh 3) 2(μ-PPh 2)Pt 2B 9H 6-3,9-( O- i-Pr) 2-11-Cl] ( 5). 簇合物 4和 5都具有Pt 2B 9多面体骨架结构, 2个Pt原子位于敞开的Pt 2B 3面上的相邻位置, 且由一个PPh 2基团桥连, 每个Pt原子还与3个B原子和一个PPh 3基团中的P原子成键. 通过红外光谱、元素分析、X射线单晶衍射对5个簇合物进行了结构表征. 相似文献
7.
The reaction of [PtCl 2(PPh 3) 2] with closo‐B 10H 102? in ethanol under reflux conditions gave two nido 11‐vertex platinaundecaborane clusters: [(PPh 3) 2PtB 10H 10‐8,10‐(OEt) 2]·CH 2Cl 2 (1) and [(PPh 3) 2PtB 10H 11‐11‐OEt]·CH 2Cl 2 (2) . A novel B 10H 102? deboronated nido 11‐vertex diplatinaundecaborane [(µ‐PPh 2)(PPh 3) 2Pt 2B 9H 6‐3,9,11‐(OEt) 3]·CH 2Cl 2 (3) was obtained when the same reaction was carried out under solvothermal conditions. All of these compounds were characterized by infrared spectroscopy, NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. Both clusters 1 and 2 have a nido 11‐vertex {PtB 10} polyhedral skeleton in which the Pt atom lies in the open PtB 4 face. Each Pt atom connects with four B atoms and two P atoms of the PPh 3 ligands. Cluster 3 has a nido 11‐vertex {Pt 2B 9} polyhedral skeleton in which two Pt atoms sit in neighbouring positions of the open Pt 2B 3 face, bridged by a PPh 2 group. Each Pt atom connects three B atoms and a P atom of the PPh 3 ligand. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
8.
A tetranuclear gold cluster has been synthesized by the reaction of [Au(PPh 3)NO 3] with the closo carborane diphosphine 1,2-(PPh 2) 2-1,2-C 2B 10H 10 in THF, and characterized by elemental analysis, FT-IR, 1H and 13C?NMR spectroscopy and X-ray structure determination. The cluster crystallizes in the triclinic Pī, a?=?15.118(8)?Å, b?=?16.057(9)?Å, c?=?24.284(13)?Å, α?=?80.822(9)°, β?=?79.624(8)°, γ?=?81.938(8)°, Z?=?2, R 1?=?0.0626, wR 2?=?0.1894. A single crystal structure determination showed that four gold atoms form a tetrahedral framework. Among these four gold atoms, two were chelated by two nido carborane diphosphine [7,8-(PPh 2) 2-7,8-C 2B 9H 10] ? anions coming from the degradation of the initial closo ligand 1,2-(PPh 2) 2-1,2-C 2B 10H 10, while the other two were ligated to two PPh 3 groups. The luminescence of this cluster was also investigated in dichloromethane solution at room temperature. 相似文献
9.
Solvothermal synthesis method has been successfully introduced into the diphosphine carborane system, and two new nickel complexes
containing nido-carborane diphosphine ligand [7,8-(PPh 2) 2-7,8-C 2B 9H 10] − with the formula [Ni 2(μ-Cl)(μ-OOPPh 2){7,8-(PPh 2) 2-7,8-C 2B 9H 10} 2]·CH 2Cl 2 ( 1) and [H 3O][NiBr 2] {7,8-(PPh 2) 2-7,8-C 2B 9H 10}·C 6H 6 ( 2) were obtained by the reactions of 1,2-(PPh 2) 2-1,2-C 2B 10H 10 with NiCl 2·6H 2O or NiBr 2·6H 2O in CH 2Cl 2 under the solvothermal condition. Both of the two complexes have been characterized by the elemental analysis, FT-IR, 1H and 13C NMR spectroscopy and single crystal X-ray diffraction. The X-ray structure analysis for these two complexes reveals the
nido-nature of the carborane diphosphine ligand, indicating that the solvothermal synthesis is an efficient method for the degradation
of the closo-carborane diphosphine ligand. 相似文献
10.
In toluene at reflux temperatures [Ru 3(CO) 12] and 7-SMe 2- nido-7-CB 10H 12 give the charge-compensated cluster complex [1-SMe 2-2,2-(CO) 2-7,11-(μ-H) 2-2,7,11-Ru 2(CO) 6- closo-2,1-RuCB 10H 8] ( 1) . Treatment of 1 with dppm in THF affords [1-SMe 2-2,2-(CO) 2-7,11-(μ-H) 2-2,7,11-Ru 2(μ -dppm)(CO) 4- closo-2,1-RuCB 10H 8] ( 2) [dppm = bis(diphenylphosphino)methane; THF = tetrahydrofuran]. The latter complex on heating in THF with [
]F yields the salt [
][1-SMe-2,2-(CO) 2-7,11-(μ-H) 2-2,7,11-Ru 2(μ -dppm)(CO) 4- closo-2,1-RuCB 10H 8] ( 3). Reaction of 3 with [AuCl(PPh 3)] and Tl[PF 6] gives the neutral zwitterionic complex [1-S(Me)Au (PPh 3)-2,2-(CO) 2-7,11-(μ-H) 2-2,7,11-Ru 2(μ-dppm)(CO) 4- closo-2,1-RuCB 10H 8] ( 4). The structures of 1, 3 and 4 were determined by single-crystal X-ray diffraction studies.*Dedicated to Professor F. Albert Cotton on the occasion of his 75th birthday, in appreciation of our long friendship and in recognition of his outstanding contributions to the study of complexes with metal–metal bonds. 相似文献
11.
Electrophilic deuteration of closo-[1-CB 11H 12] − in the DCl/D 2O system confirmed the expected order of reactivity on individual skeletal atoms, decreasing in the series B(12) > B(7–11) > B(2–6) > C(1). In contrast, electrophilic B-substitution of closo-[1-CB 11H 12] − with H 2NOSO 3H is consistent with the preference of the B(7)-substitution to suggest a different mechanism for almost exclusive formation of 7-H 3N- closo-1-CB 11H 11. 7-Me 3N- closo-1-CB 11H 11 was isolated along with the remaining 2- and 12-Me 3N-1-CB 11H 11 isomers as side products of the thermal decomposition of [BH 2(NMe 3) 2] +[ nido-7-CB 10H 13] − at 270°C, which is inconsistent with a specific insertion of the BNMe 3 fragment into the open face of nido-[7-CB 10H 13] −. Nevertheless, clean 10B-insertion was observed in the reactions of Et 3N 10BH 3 with both nido-[7-CB 10H 13] − and 7-Me 3N- nido-7-CB 10H 12 to give respectively closo-[1-CB 11H 12] − and [1-Me 2N-1-CB 11H 11] − labelled by 10B exclusively at the B(2) site. Cage rearrangement was observed, however, in the reaction of 7-Me 3N-8-PhCH 2- nido-7-CB 10H 11 with Et 3NBH 3 under similar conditions to produce only the 1-Me 3N-7-PhCH 2-1-CB 11H 10 closo-isomer. 相似文献
12.
Chelate exo- nido-ruthenacarboranes exo-5,6,10-[RuCl(Ph 2P(CH 2) 4PPh 2)]-5,6,10-(μ-H) 3-10-H-7,8-R,R′- nido-7,8-C 2B 9H 6 (R, R′ = H, PhCH 2) were synthesized by the direct method using the reaction of Cl 2Ru(PPh 3)(Ph 2P(CH 2) 4PPh 2) with [7,8-R,R′- nido-7,8-C 2B 9H 10][K] in benzene. Unsubstituted exo-nido-ruthenacarborane (R, R′ = H) was used in situ for the synthesis of the dinuclear Ru-Cu exo-closo cluster of the formula exo-closo-(Ph 3P)Cu(μ-H)Ru(Ph 2P(CH 2) 4PPh 2)(η 5-C 2B 9H 11). The isomerism of the complex and the crystal structure were studied by NMR spectroscopy and X-ray diffraction. The catalytic activity of the cluster in the atom transfer radical polymerization of methyl methacrylate was investigated. 相似文献
13.
Ruthenium(ii) and (iii) carborane complexes containing XantPhos as a ligand were synthesized for the first time. It was shown that the reaction of the known complex exo-5,6,10-[Cl(Ph3P)2Ru]-5,6,10-(µ-H)3-10-H-nido-7,8-C2B9H8 with a 10% molar excess of XantPhos in benzene at 80 °C leads to a new closo-ruthenacarborane 3-Cl-3,3-[x2-XantPhos]-closo-3,1,2-RuC2B9H11, which can be easily converted to the corresponding acetonitrile complex 3-CH3CN-3,3-[x2-XantPhos]-closo-3,1,2-RuC2B9H11 by the reaction with isopropylamine in a dichloromethane—acetonitrile solvent mixture at 40 °C. These compounds, as well as previously synthesized ruthenium(ii) carborane complexes, were used as a basis for new catalyst systems allowing to conduct controlled radical polymerization at high rates even at low catalyst loading. The specific features of methyl methacrylate polymerization under the action of the indicated catalyst systems were considered and the mechanism of the process was investigated. 相似文献
14.
New hetero-substituted charge-compensated cobalt bis(1,2-dicarbollide) derivatives were synthesized by the reaction of 8,8′-μ-iodo-3- commo-3-cobalta-bis(1,2-dicarba- closo-dodecaborane) [8,8′-μ-I-3,3′-Co(1,2-C 2B 9H 10) 2] with 1,4-thioxane, pyridine N-oxide, and tetrahydropyran. X-ray diffraction studies showed that the 8′-iodo-8-(pyridiniumoxy)eucosahydro-1,1′,2,2′-tetracarba-3- commo-cobalta- closo-tricosaborate molecule has the gauche-conformation (the substituents are turned with respect to each other by 69.2°). The positive charge is predominantly localized on the N(Py) atom. 相似文献
15.
The molybdacarboranes [3-{L-κ 2N,N}-3-(CO) 2- closo-3,1,2-MoC 2B 9H 11] (L=2,2′-bipyridine (2,2′-bpy, 1 a ) or 1,10-phenanthroline (1,10-phen, 1 b )) incorporating well-known potentially non-innocent ligands (CO, 2,2′-bpy, 1,10-phen) and the “non-spectator” nido-carborane ([η 5-C 2B 9H 11] 2−) ligand were prepared and fully characterised. High-resolution mass spectrometry, single-crystal X-ray diffraction methods, spectroscopy (IR, (resonance) Raman, NMR), cyclic voltammetry and spectroelectrochemistry (electrochemical properties) were supported by theoretical investigations of the electronic structure (DFT, CAS-SCF, TD-DFT). 相似文献
16.
Treatment of [1,1-(PPh 3) 2- closo-1-RuB 10H 8-2, 3-(OEt) 2] 1) 1 with the more basic ligand PMe 3 readily results in the displacement of PPh 3 to form the hitherto unreported mixed ligand compound [1,1-(PMe 3) (PPh 3)- closo-1-RuB 10H 8-2, 3-(OEt) 2] 2 , which is characterized by singlecrystal X-ray diffraction analysis. Crystals are monoclinic, space group P2 1, with a = 1059.2(2), b = 1291.5(2), c = 1187.6(2) pm, β = 91.56(1)°, Z = 4; the final R factor is 0.0198 for 3303 observed reflections [I>2.0 s?(I)]. Compound 2 is also characterized by detailed multielement, multiple resonance, and multidimensional n.m.r. spectroscopy ( 1H, 1H-{ 11B}, [ 1H– 1H]{ 11B}-COSY, 11B, 11B-{ 1H}, and 31P). 相似文献
17.
The replacement of the PPh 3 ligands in “three-bridge” exo-nido-ruthenacarborane 5,6,10-[RuCl(PPh 3) 2]-5,6,10-(μ-H) 3-10-H- exo-nido-7,8-C 2B 9H 8 with diphosphines, viz., 1,3-bis(diphenylphosphino)propane (dppp) or 1,4-bis(diphenylphosphino)butane (dppb) dramatically decreases the barrier to
the thermal exo-nido→closo rearrangement affording the chelate closo-complexes 3,3-[Ph 2P(CH 2) nPPh 2]-3-H-3-Cl- closo-3,1,2-RuC 2B 9H 11 ( n = 3 or 4) under mild conditions. In the reaction with dppp, the rearrangement is accompanied by the formation of 17-electron
paramagnetic closo-ruthenacarborane 3,3-[Ph 2P(CH 2) 3PPh 2]-3-Cl- closo-3,1,2-RuC 2B 9H 11, which could be isolated as the main product when the reaction was carried out at 80 °C.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2455–2459, November, 2005. 相似文献
18.
The first primary 2‐aminocarba‐ closo‐dodecaborates [1‐R‐2‐H 2N‐ closo‐CB 11H 10] ? (R=H ( 1 ), Ph ( 2 )) have been synthesized by insertion reactions of (Me 3Si) 2NBCl 2 into the trianions [7‐R‐7‐ nido‐CB 10H 10] 3?. The difunctionalized species [1,2‐(H 2N) 2‐ closo‐CB 11H 10] ( 3 ) and 1‐CyHN‐2‐H 3N‐ closo‐CB 11H 10 (H‐ 4 ) have been prepared analogously from (Me 3Si) 2NBCl 2 and 7‐H 3N‐7‐ nido‐CB 10H 12. In addition, the preparation of [Et 4N][1‐H 2N‐2‐Ph‐ closo‐CB 11H 10] ([Et 4N]‐ 5 ) starting from PhBCl 2 and 7‐H 3N‐7‐ nido‐CB 10H 12 is described. Methylation of the [1‐Ph‐2‐H 2N‐ closo‐CB 11H 10] ? ion ( 2 ) to produce 1‐Ph‐2‐Me 3N‐ closo‐CB 11H 10 ( 6 ) is reported. The crystal structures of [Et 4N]‐ 2 , [Et 4N]‐ 5 , and 6 were determined and the geometric parameters were compared to theoretical values derived from DFT and ab initio calculations. All new compounds were studied by NMR, IR, and Raman spectroscopy, MALDI mass spectrometry, and elemental analysis. The discussion of the experimental NMR chemical shifts and of selected vibrational band positions is supported by theoretical data. The thermal properties were investigated by differential scanning calorimetry (DSC). The p Ka values of 2‐H 3N‐ closo‐CB 11H 11 (H‐ 1 ), 1‐H 3N‐ closo‐CB 11H 10 (H‐ 7 ), and 1,2‐(H 3N) 2‐ closo‐CB 11H 10 (H 2‐ 3 ) were determined by potentiometric titration and by NMR studies. The experimental results are compared to theoretical data (DFT and ab initio). The basicities of the aminocarba‐ closo‐dodecaborates agree well with the spectroscopic and structural properties. 相似文献
19.
The Raman and IR spectra of the cesium salts of monocarbon carboranes, [ closo-CB 11H 12] – and [ nido-CB 10H 13] –, are reported and the assignment of the normal modes is given. Quantum-chemical calculations of the geometry of undistorted closo-anions B 12H 12
2– and CB 11H 12
– were carried out and normal coordinate analysis for the latter was performed. Structural parameters and spectral characteristics of isoelectronic closo-polyhedra [B 12H 12] 2–, [CB 11H 12] –, and p-C 2B 10H 12 and those of the closo- and nido-structures were compared. 相似文献
20.
A new approach to synthesis of hetero-substituted derivatives of cobalt bis(1,2-dicarbollide) was proposed. The approach involves stepwise introduction of functional groups into different dicarbollide ligands. Halogenation of the monohydroxy derivative [8-OH-3,3??-Co-(1,2-C 2B 9H 10)(1??,2??-C 2B 9H 11)] ? gave the corresponding halogen hydroxy derivatives [8-OH-8??-X-3,3??-Co(1,2-C 2B 9H 10) 2] ? (X = Cl, Br, and I). Reactions of 8,8??-??-iodonium-3- commo-cobaltbis(1,2-dicarba- closo-dodecaborate) [8,8??-I-3,3??-Co(1,2-C 2B 9H 10) 2] with chloroform and 1,2-dibromoethane yielded the mixed halides [8-Y-8??-I-3,3??-Co(1,2-C 2B 9H 10) 2] ? (Y = Cl and Br). 相似文献
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