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1.
Reaction of [Mn(NCMe)3(CO)3][PF6] with Li3[7-NHBut-nido-7-CB10H10] in THF (THF = tetrahydrofuran) affords the twelve-vertex manganacarborane dianion [1-NHBut-2,2,2-(CO)3-closo-2,1-MnCB10H10]2−, isolated as the bis-[N(PPh3)2]+ salt (5a). This species reacts with {Pt(dppe)}2+ (dppe = Ph2PCH2CH2PPh2) to afford the bimetallic complex [1-NH2But-2,3-{Pt(dppe)}-2,2,2-(CO)3-closo-2,1-MnCB10H9] (7) which has an Mn-Pt bond. In contrast, with {Cu(PPh3)}+ the anion of 5a yields a CuMnCu trimetallic compound [1-{NH(But)Cu(PPh3)}-2,3,7-{Cu(PPh3)}-3,7-(μ-H)2-2,2,2-(CO)3-closo-2,1-MnCB10H8] (8) in which one of the Cu centers is bonded to Mn, whilst the other is attached to the pendant NHBut group. Upon treatment with Ag+, compound 5a is oxidized giving the very unusual Mn(III)-carbonyl complex [1,2-μ-NHBut-2,2,2-(CO)3-closo-2,1-MnCB10H10] (9a) in which the carborane ligand formally acts as an eight-electron donor to manganese. The novel structural features of compounds 7, 8, and 9a have been confirmed by X-ray diffraction studies.  相似文献   

2.
The reaction between [5-I-7,8-Ph2-7,8-nido-C2B9H8]2− and NiCl2(dppe) affords 1,2-Ph2-4,4-dppe-12-I-4,1,2-closo-NiC2B9H8 (1) and 1,8-Ph2-2,2-dppe-10-I-2,1,8-closo-NiC2B9H8 (2). Reaction between the same carborane ligand and cis-PtCl2(PMe2Ph)2 yields three species, 1,8-Ph2-2,2-(PMe2Ph)2-10-I-2,1,8-closo-PtC2B9H8 (3), 1,8-Ph2-2,2-(PMe2Ph)2-12-I-2,1,8-closo-PtC2B9H8 (4), and 1,8-Ph2-2,2-(PMe2Ph)2-7-I-2,1,8-closo-PtC2B9H8 (5). Compounds 1-5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC2B9 architecture of 1 constitutes a “1,2 → 1,2” cage C atom isomerisation, and the 2,1,8-MC2B9 architectures of 2-5 a 1,2 → 1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph2-3,3-L2-9-I-3,1,2-closo-MC2B9H8 [M = Ni, L2 = dppe; M = Pt, L2 = (PMe2Ph)2]. The location of the (iodide) labelled boron vertex in the products allows speculation as to the mechanism of these isomerisations and the possible involvement of triangle face rotation is discussed.  相似文献   

3.
The reaction between [7,8-Ph2-7,8-nido-C2B9H9]2− and [(η-C7H7)Mo(MeCN)3]+ affords five products. Four have been isolated and shown to be structural isomers of (η-C7H7)MoPh2C2B9H9. Compound 1 has a pseudocloso structure. In solution it gives way to the non-icosahedral compound 2 which in turn rearranges into the “1,2 → 1,7” C-atom isomerised compound 5 having a 2,1,8-MoC2B9 structure. A further “1,2 → 1,7” C-atom isomerised species, compound 4, is also isolated but has a 1,2,4-MoC2B9 architecture. Compound 4 forms via an intermediate 3, which is too unstable to characterise. Structurally the sequence of compounds 1, 2 and 5 maps well onto the sequential diamond-square-diamond isomerisation mechanism of 1,2-closo-C2B10H12 into 1,7-closo-C2B10H12 proposed by Wales. An alternative pathway from the notional first product of the metallation, 1,2-Ph2-3-(η-C7H7)-3,1,2-closo-MoC2B9H9, is required to rationalise the intermediate compound 3 and, from it, compound 4.  相似文献   

4.
Reaction of [Co(CO)3(NO)] with [2-NMe3-closo-2-CB10H10] in refluxing CH2Cl2 affords the mono- and di-cobalt complexes [1-NMe3-2-CO-2-NO-closo-2,1-CoCB10H10] (3) and [2,7-{Co(CO)(NO)}-7-(μ-H)-1-NMe3-2-CO-2-NO-closo-2,1-CoCB10H9] (4), respectively, of which 4 contains formally both Co(I) and Co(-I) centers. Compound 4 reacts with CO to give 3, or with donor ligands L in the presence of Me3NO to afford simple substituted species, [1-NMe3-2-L-2-NO-closo-2,1-CoCB10H10] (compounds 5; L = PEt3, PPh3, CNBut).  相似文献   

5.
Three group 10 complexes containing nido-carborane diphosphine, [NiCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}] (1), [PdCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}] · 1.25CH2Cl2 (2) and [PtCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}] · 2.5CH2Cl2 (3) have been synthesized by the reactions of [M(PPh3)2Cl2] (M = Ni, Pd, Pt) with closo carborane diphosphine 1,2-(PPh2)2-1,2-C2B10H10 in ethanol. For complex 3, it could also be obtained under solvothermal condition. All three complexes were characterized by elemental analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray structure determination. Single crystal structures show that their structures are similar to each other. In each complex, the nido [7,8-(PPh2)2-7,8-C2B9H10], which resulted from the degradation of the initial closo ligand 1,2-(PPh2)2-1,2-C2B10H10 during the reaction process, was coordinated bidentately through the P atoms to M(II) ion, and this resulted in a stable five-membered chelating ring between the bis-diphosphine ligand and the metal. The coordination mode of the metal can be described as a slightly distorted square-planar, in which the remaining two positions were occupied by one Cl and one PPh3 group.  相似文献   

6.
Trityl borate salts [4-RPyCPh3][B(C6F5)4] (R = H 1, tBu 2, Et 3, NMe24) and [R3PCPh3][B(C6F5)4] (R = Me 5, nBu 6, Ph[1] 7, p-MeC6H48) are readily prepared via equimolar reaction of the appropriate pyridine or phosphine and trityl borate [CPh3][B(C6F5)4]. The analogous reactions of PiPr3 affords the product [(p-iPr3P-C6H4)Ph2CH][B(C6F5)4] (9) while the corresponding reactions of Cy3P and tBu3P gave the cyclohexadienyl derivatives [(p-R3PC6H5)CPh2][B(C6F5)4] (R = Cy 10, tBu 11). X-ray structures of 5 and 9 are reported.  相似文献   

7.
4,8-Di-tert-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaborocine (1) has been prepared in high yield by the addition of H3B·SMe2 to 6,6′-methylene(2-tert-butyl-4-methylphenol). Dioxaborocine 1 is a relatively stable solid that reacts with a variety of aliphatic alkenes in the presence of catalytic amounts of [Cp*IrCl2]2 to give the terminal hydroboration products. Analogous reactions with vinylarenes, however, afford the corresponding alkenylboronate esters along with equal amounts of the hydrogenation products. Boron products have been characterized by a number of physical and analytical methods, including single-crystal X-ray diffraction studies.  相似文献   

8.
Short-bite aminobis(phosphonite) containing olefinic functionalities, PhN{P(OC6H3(OMe-o)(C3H5-p))2}2 (1) was synthesized by reacting PhN(PCl2)2 with eugenol in the presence of triethylamine. The ligand 1 acts as a bidentate chelating ligand toward metal complexes [M(CO)4(C5H10NH)2] forming [M(CO)42-PhN{P(OC6H3(OMe-o)(C3H5-p))2}2}] (M = Mo, 2; W, 3). The reaction between 1 and [CpFe(CO)2]2 leads to the cleavage of one of the P-N bonds due to the metal assisted hydrolysis to give a mononuclear complex [CpFe(CO){P(O)(OC6H3(OMe-o)(C3H5-p))2}{PhN(H)(P(OC6H3(OMe-o)(C3H5-p))2)}] (4). Treatment of 1 with gold(I) derivative, [AuCl(SMe2)] resulted in the formation of a dinuclear complex, [(AuCl)2{PhN{P(OC6H3(OMe-o)(C3H5-p))2}2}] (5) with a Au···Au distance of 3.118(2) Å indicating the possibility of aurophilic interactions. An equimolar reaction between 1 and [Ru(η6-p-cymene)Cl2]2 afforded a tri-chloro-bridged bimetallic complex [(η6-p-cymene)Ru(μ-Cl)3Ru{PhN(P(OC6H3(OMe-o)(C3H5-p))2)2}Cl] (6). The crystal structures of 1-3 and 5 were established by single crystal X-ray diffraction studies.  相似文献   

9.
A new class of amidoalkyl dibenzofuranols and 1H-benzo[2,3]benzofuro[4,5-e][1,3]oxazin-3(2H)-ones was synthesized in very good yields through polyphosphoric acid supported on silica (PPA-SiO2) catalyzed one-pot three component condensation of 2-dibenzofuranol; aromatic aldehydes and acetamide or benzamide or urea under solvent free conditions. At 125 °C the reaction led to the formation of amidoalkyl dibenzofuranols 5a-k where as at 160 °C cyclization take place to give oxazin-3(2H)-one analogues 6a-e. Screening all the 16 compounds for in vitro antimycobacterial activity against Mycobacterium tuberculosis H37Rv (MTB) resulted 1-((4-chlorophenyl)(2-hydroxydibenzo[b,d]furanyl)methyl)urea 5h; 1-((4-bromophenyl)(2-hydroxydibenzo[b,d]furanyl)methyl)urea 5i; 1-phenyl-1H-benzo[2,3]benzo furo[4,5-e][1,3]oxazin-3(2H)-one 6a (MIC 3.13 μg/mL) and 1-(4-chlorophenyl)-1H-benzo[2,3]benzofuro[4,5-e][1,3]oxazin-3(2H)-one 6b; 1-(4-bromophenyl)-1H-benzo[2,3]benzofuro [4,5-e][1,3]oxazin-3(2H)-one 6c (MIC 1.56 μg/mL) as most active antitubercular agents.  相似文献   

10.
Photolysis of the molybdaborane [(η5-C5H5)(η51-C5H4)-arachno-2-MoB4H7] (1) in benzene-d6 gives ca. 60% conversion to the compound [(η5-C5H5)(η51-C5H4)-nido-2-MoB4H5] (2). Compound 2 could not be isolated as a solid and is thermally unstable at 20 °C in solution with a half-life of 3-4 h. Repeated photolysis and thermolysis of 1 in the presence of BH3 · thf gives a low yield of the known metallacarbaborane [(η5-C5H5)(η23-C3H3)-closo-1-MoC2B9H9] (3) suggesting that 3 is formed from 1 via 2. Reaction of 1 with PEt3 gives initially [(η5-C5H5)(η51-C5H4)-arachno-2-MoHB4H4PEt3] (4). Longer reaction times (>10 min, 20 °C) give in addition [(η5-C5H5)(η51-C5H4)-arachno-1-MoHB3H3PEt3] (5). Both 4 and 5 are unstable in solution or the solid state decomposing to the molybdacarbaborane [(η5-C5H5)(η32- C3H3)-nido-1-MoC2B3H5] (6), [Mo(η-C5H5)2H2] and BH3 · PEt3. Compound 1 is deprotonated cleanly by KH in thf at the Mo-H-B bridging proton to give (7).  相似文献   

11.
Reaction of [Mo2O2(μ-S)2(H2O)6]2+ with Mo(CO)6 or metallic Mo under hydrothermal conditions (140 °C, 4 M HCl) gives oxido-sulfido cluster aqua complex [Mo33-S)(μ-O)2(μ-S)(H2O)9]4+ (1). Similarly, [W33-S)(μ-O)2(μ-S)(H2O)9]4+ (2) is obtained from [W2O2(μ-S)2(H2O)6]2+ and W(CO)6. While reaction of [Mo2O2(μ-S)2(H2O)6]2+ with W(CO)6 mainly proceeds as simple reduction to give 1, [W2O2(μ-S)2(H2O)6]2+ with Mo(CO)6 produces new mixed-metal cluster [W2Mo(μ3-S)(μ-O)2(μ-S)(H2O)9]4+ (3) as main product. From solutions of 1 in HCl supramolecular adduct with cucurbit[6]uril (CB[6]) {[Mo3O2S2(H2O)6Cl3]2CB[6]}Cl2⋅18H2O (4) was isolated and structurally characterized. The aqua complexes were converted into acetylacetonates [M3O2S2(acac)3(py)3]PF6 (M3 = Mo3, W3, W2Mo; 5a-c), which were characterized by X-ray single crystal analysis, electrospray ionization mass spectrometry and 1H NMR spectroscopy. Crystal structure of (H5O2)(Me4N)4[W33-S)(μ2-S)(μ2-O)2(NCS)9] (6), obtained from 2, is also reported.  相似文献   

12.
Two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] 1 and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO4 and HPO2(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO4 and HPO3 units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.  相似文献   

13.
The dinuclear bis(6-X-pyridin-2-olato) ruthenium complexes [Ru2(μ-XpyO)2(CO)4(PPh3)2] (X = Cl (4B) and Br (5B)), [Ru2(μ-XpyO)2(CO)4(CH3CN)2] (X = Cl (6B), Br (7B) and F (8B)) and [Ru2(μ-ClpyO)2(CO)4(PhCN)2] (9B) were prepared from the corresponding tetranuclear coordination dimers [Ru2(μ-XpyO)2(CO)4]2 (1: X = Cl; 2: X = Br) and [Ru2(μ-FpyO)2(CO)6]2 (3) by treatment with an excess of triphenylphosphane, acetonitrile and benzonitrile, respectively. In the solid state, complexes 4B-9B all have a head-to-tail arrangement of the two pyridonate ligands, as evidenced by X-ray crystal structure analyses of 4B, 6B and 9B, in contrast to the head-to-head arrangement in the precursors 1-3. A temperature- and solvent-dependent equilibrium between the yellow head-to-tail complexes and the red head-to-head complexes 4A-7A and 9A, bearing an axial ligand only at the O,O-substituted ruthenium atom, exists in solution and was studied by NMR spectroscopy. Full 1H and 13C NMR assignments were made in each case. Treatment of 1 and 2 with the N-heterocyclic carbene (NHC) 1-butyl-3-methylimidazolin-2-ylidene provided the complexes [Ru2(μ-XpyO)2(CO)4(NHC)], X = Cl (11A) or Br (12A). An XRD analysis revealed the head-to-head arrangement of the pyridonate ligands and axial coordination of the carbene ligand at the O,O-substituted ruthenium atom. The conversion of 11A and 12A into the corresponding head-to-tail complexes was not possible.  相似文献   

14.
The reaction of Re(CO)5Cl with o- or p-N-(nitrophenyl)ethylenediaminediacetic acid (H2L1, H2L2) and o- or p-N-(nitrophenyl)propylenediaminediacetic acid (H2L3, H2L4) in methanol leads to the formation of stable anionic [Et3NH][Re(CO)3(L)] · H2O complexes 1-4. These compounds have been characterized by means of IR, mass spectrometry, elemental analysis, NMR and conductimetry, as well as X-ray crystallography for 2 and 3. The [Re(CO)3]+ moiety is coordinated via the nitrogen of the iminodiacetic acid unit and two oxygens of monodentate carboxylate groups. In each case, the nitro group of the aromatic ring remains uncoordinated. The analogous technetium-99m complexes 1′ and 3′ were also prepared quantitatively by the reaction of H2L1 and H2L3, respectively, with the fac-[99mTc(CO)3(H2O)3]+ precursor in ethanol. The corresponding Re and 99mTc compounds were shown to possess the same structure by means of HPLC studies. The high affinity of these ligands for the Tc(I) or Re(I) core, coupled with the easiness of their derivatization (by reduction of the nitro group in amino group), implies that the utilization of this ligand system to develop target-specific radiopharmaceuticals for diagnosis and therapy is promising.  相似文献   

15.
The orthorhombically crystallizing salts Rb2[B12(OH)12]·2H2O (= 1576.81(9), b = 813.08(5), c = 1245.32(7) pm) and Rb2[B12(OH)12]·2H2O2 (= 1616.54(9), b = 814.29(5), c = 1260.12(7) pm) could be prepared from Rb2[B12H12] and hydrogen peroxide. Both crystal structures were determined by X-ray single crystal diffraction and refined in the space group Cmce. They are not isostructural to the other compounds containing icosahedral dodecahydroxo-closo-dodecaborate dianions [B12(OH)12]2− and potassium, rubidium or cesium cations already known to literature, but both title compounds crystallize quasi-isotypically exhibiting Rb+ cations in 10-fold oxygen coordination. The hydrogen peroxide adduct (Rb2[B12(OH)12]·2H2O2) is explosive on shock and heat, while the hydrate (Rb2[B12(OH)12]·2H2O) is not.  相似文献   

16.
The new aryl phosphinites PPh2OR (R = 2,4,6-Me3C6H2, 1; R = 2,6-Ph2C6H3, 2) have been prepared from chlorodiphenylphosphine and the corresponding phenols. In these ligands, the ortho-positions of the aromatic phosphite function are blocked by methyl and phenyl substituents, which allows coordination to metal centres without ortho-metallation. Thus, reaction with [PdCl2(cod)] leads to the complexes trans-[PdCl2(PPh2OR)2] (R = 2,4,6-Me3C6H2, 3; R = 2,6-Ph2C6H3, 4), while the reaction with [Rh2(CO)4Cl2] gives trans-[Rh(CO)Cl(PPh2OR)2] (R = 2,4,6-Me3C6H2, 5; R = 2,6-Ph2C6H3, 6). The single-crystal X-ray structure analyses of 3 and 5 confirm the trans-coordination of the new ligands in these square-planar complexes.  相似文献   

17.
The iron hydrido complex HFe(CO)2{P(OPh)3}{(PhO)2POC6H4} (1), was rapidly deprotonated by DBU or [BzMe3N][OH] in THF to afford the new carbonyl iron anion [Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}] ([2]), containing an ortho-metallated triphenyl phosphite ligand. Complex [2] reacted with triorganostannyl and plumbyl salts and with halogens to give the octahedral FeII compounds Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}(X) (X=SnPh3, 3; SnMe3, 4; PbPh3, 5; PbMe3, 6; Cl, 7; Br, 8; I, 9). The Group 14 complexes 3-6 were obtained in one isomeric form in which the PIII-donor atoms are mutually cis, the carbonyl ligands are cis and the P(OPh)3 and MR3 (M=Sn, Pb; R=Ph, Me) groups are trans as determined by solution-state IR, 31P and 13C NMR spectroscopic data. This geometry was confirmed for 3 by a single crystal X-ray diffraction study. The halide complexes, however, were obtained as a mixture of isomers. The major isomer (7, X=Cl; 8a, X=Br; 9a, X=I) has cis P atoms, trans CO groups and the halide located trans to the phosphorus atom of the ortho-metallated phosphite ligand. The structure of 9a was confirmed by an X-ray diffraction study. Two other isomers, designated 8b (X=Br) and 9b (X=I), with cis P atoms and cis CO groups were isolated from the reactions of [2] with Br2 and I2, respectively. The structure of the latter was established by X-ray crystallography and is related to 9a by exchange of the P(OPh)3 ligand and a carbonyl group such that the metal-bound C atom of the five-membered metallacycle is trans to CO. The stereo-geometry of 8b could not be unambiguously assigned from the spectroscopic data; however, two of the seven possible geometric isomers were suggested as plausible structures.  相似文献   

18.
Two complexes of gold of the compositions [Au(DMG)ClPy] (1) and [AuCl2Py2][AuCl4] · 2[AuCl3Py] (2), where H2DMG was dimethylglyoxime, were synthesized as the products of interaction of H[AuCl4] · 4H2O with H2DMG in the presence of pyridine and characterized by X-ray structural analysis. It was shown that depending on the synthetic conditions, the final product represents a molecular complex 1 or an ionic complex 2, in the latter one the charged and neutral species being combined via Au?Cl or Au?Au interactions.  相似文献   

19.
A novel organic-inorganic hybrid pentaborate [Ni(C4H10N2)(C2H8N2)2][B5O6(OH)4]2 has been synthesized by hydrothermal reaction and characterized by FT-IR, Raman spectroscopy, elemental analyses and DTA-TGA. Its crystal structure was determined from single crystal X-ray diffraction. The structure consists of isolated polyborate anion [B5O6(OH)4] and nickel complex cation of [Ni(C4H10N2)(C2H8N2)2]2+, in which the two kinds of ligands come from the decomposition of triethylenetriamine material. The [B5O6(OH)4] units are connected to one another through hydrogen bonds, forming a three-dimensional framework with large channel along the a and c axes, in which the templating [Ni(C4H10N2)(C2H8N2)2]2+ cations are located. The assignments of the record FT-IR absorption frequencies and Raman shifts were given.  相似文献   

20.
The organotin complex [Ph3SnS(CH2)3SSnPh3] (1) was synthesized by PdCl2 catalyzed reaction between Ph3SnCl and disodium-1,3-propanedithiolate which in turn was prepared from 1,2-propanedithiol and sodium in refluxing THF. Reaction of 1 with Ru3(CO)12 in refluxing THF affords the mononuclear complex trans-[Ru(CO)4(SnPh3)2] (2) and the dinuclear complex [Ru2(CO)6(μ-κ2-SCH2CH2CH2S)] (3) in 20 and 11% yields, respectively, formed by cleavage of Sn-S bond of the ligand and Ru-Ru bonds of the cluster. Treatment of pymSSnPPh3 (pymS = pyrimidine-2-thiolate) with Ru3(CO)12 at 55-60 °C also gives 2 in 38% yield. Both 1 and 2 have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction analysis.  相似文献   

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