共查询到20条相似文献,搜索用时 15 毫秒
1.
Photolysis of the molybdaborane [(η5-C5H5)(η5:η1-C5H4)-arachno-2-MoB4H7] (1) in benzene-d6 gives ca. 60% conversion to the compound [(η5-C5H5)(η5:η1-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)(η2:η3-C3H3)-closo-1-MoC2B9H9] (3) suggesting that 3 is formed from 1 via 2. Reaction of 1 with PEt3 gives initially [(η5-C5H5)(η5:η1-C5H4)-arachno-2-MoHB4H4PEt3] (4). Longer reaction times (>10 min, 20 °C) give in addition [(η5-C5H5)(η5:η1-C5H4)-arachno-1-MoHB3H3PEt3] (5). Both 4 and 5 are unstable in solution or the solid state decomposing to the molybdacarbaborane [(η5-C5H5)(η3:η2- 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
2.
M. Cristina Cassani 《Inorganica chimica acta》2005,358(5):1595-1604
The preparation of a series of 1,2-phenylenedioxoborylcyclopentadienyl-metal complexes is described. These are of formula [M{η5-C5H4(BX)}Cl3] [M = Ti and X = CAT (2a), CATt (2b) or CATtt (2c); X = CATtt and M = Zr (4a) or Hf (4b)], [M{η5-C5H4(BX)}2Cl2] [M = Zr, X = CAT (3a) or CATt (3c); or M = Hf, X = CAT (3b) or CATt (3d)], [M{(μ-η5-C5H3BCAT)2 SiMe2}Cl2] [M = Zr (5a) or Hf (5b)], [M{η5-C5H3(BCAT)2}Cl3] [M = Zr (6a) or Hf (6b)], [M{η5-C5H4BCAT}3(THF)] [M = La (7a), Ce (7b) or Yb (7c)], [Sn{η5-C5 H4(BCATt)}Cl](8) and [Fe{η5-C5H4(BCATt)}2] (9). The abbreviations refer to BO2C6H4-1,2 (BCAT) and the 4-But (BCATt) and the (BCATtt) analogues. The compounds 2a-9 have been characterised by microanalysis, multinuclear NMR and mass spectra. The single crystal X-ray structure of the lanthanum compound 7a is presented. 相似文献
3.
Antonio Antiñolo Rafael Fernández-Galán Antonio Otero Ana M. Rodríguez 《Inorganica chimica acta》2010,363(13):3489-3497
New C-ansa-zirconocene complexes containing methoxythiophenolate and mercaptophenolate ligands have been synthesized and characterized. The reaction of (HSC6H4-n-OMe) (n = 2, 3 or 4) with [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Me2] (1) led to the formation of monosubstituted complexes [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Me(κ,S-SC6H4-n-OMe)] (n = 2 (2); n = 3 (3)) and the disubstituted complex [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}(κ,S-SC6H4-4-OMe)2] (4). The complexes [Zr{(R)HC(η5-C5Me4)(η5-C5H4)}(κ,O-OC6H4-4-SH)2] (R = t-Bu (6); R = CH2CHCH2 (7)) and [Zr(η5-C5H4)2(OC6H4-n-SH)2] (n = 3 (9); n = 4 (10)) have been synthesized using the corresponding dimethyl zirconocene and mercaptophenol. However, the reaction of [Zr{(t-Bu)HC(η5-C5Me4)(η5-C5H4)}Cl2] (11) with 4-mercaptophenol in the presence of NEt3 led to the formation of the first example of a homoleptic six-coordinate mercaptophenolate complex of zirconium, namely [HNEt3]2[Zr(κ,O-OC6H4-4-SH)6] (12). Complex 12 can be obtained in higher yield by the reaction of ZrCl4 with six equivalents of 4-mercaptophenol and NEt3. The reaction of 12 with [Zr(η5-C5H4)2Cl2] gave the unexpected disubstituted complex [Zr(η5-C5H4)2(OC6H4-4-SH)2] (10). The molecular structures of 4 and 12 have been determined by single-crystal X-ray diffraction studies. 相似文献
4.
Santiago Gómez-Ruiz Sanjiv Prashar Mariano Fajardo Antonio Otero 《Inorganica chimica acta》2009,362(4):1042-3345
The ansa-titanocene complexes, [Ti{Me2Si(η5-C5Me4)(η5-C5H3R)}Cl2] (R = Me (5), iPr (6), tBu (7), SiMe3 (8)), were obtained from the reaction of Li2{Me2Si(C5Me4)(C5H3R)} (R = Me (1), iPr (2), tBu (3), SiMe3 (4)) with [TiCl4(THF)2], respectively. Compounds 5-8 have been tested as catalysts in the polymerization of ethylene and compared with the ansa-titanocene complexes [Ti{Me2Si(η5-C5H4)2}Cl2] and [Ti{Me2Si(η5-C5Me4)(η5-C5H4)}Cl2]. The resulting polyethylene showed molecular weights of about 200 000 g mol−1 and polydispersity values of approximately 3. In addition, the molecular structure of 6 has been determined by single crystal X-ray diffraction studies. 相似文献
5.
The reaction of [C5H4(CH2)nX]Tl (1: n = 2, X = NMe2, OMe, CN; n = 3, X = NMe2) with [(η6-C6H6)RuCl(μ-Cl)]2, 2, afforded the sandwich compounds [{η5-C5H4(CH2)nX}Ru(η6-C6H6)]PF6, 3, and [η5-C5H4(CH2)nX]2Ru, 4. Photolytic cleavage of 3 in acetonitrile afforded the tethered products [{η5:κN-C5H4(CH2)nX}Ru(CH3CN)2]PF6, 5. 相似文献
6.
Reactions of [PPh4][(η5-C5Me5)WS3] with equimolar M′Cl2 (M′ = Zn, Cd) in MeCN or 0.5 equiv. of HgCl2 in DMF afforded two binuclear clusters [PPh4][(η5-C5Me5)WS3(M′Cl2)] (1: M′ = Zn; 2: M′ = Cd) and one trinuclear cluster [{(η5-C5Me5)WS3}2Hg] (3). Compounds 1-3 were characterized by elemental analysis, IR, UV-Vis, 1H NMR and X-ray crystallography. Compound 1 may be viewed as a 1:1 composite of [PPh4][(η5-C5Me5)WS3] and ZnCl2, in which one [(η5-C5Me5)WS3]− anion binds a ZnCl2 moiety via two μ-S atoms. In the structure of 3, two [(η5-C5Me5)WS3]− anions coordinate the central Hg atom via two μ-S atoms, forming an unique bent linear structure. In addition, internal redox reactions of [PPh4][(η5-C5Me5)WS3] under the presence of M′Cl2 (M′ = Zn, Cd, Hg) in high concentrations were discussed. 相似文献
7.
The 2-methallyl complex [(η5-C9H7)Ru(η3-2-MeC3H4)(PPh3)] (3), prepared from [(η5-C9H7)Ru(PPh3)2Cl] (2) and 2-MeC3H4MgCl, reacts with HX (X = Cl, CF3CO2) in the presence of ethene to give the chiral-at-metal compounds [(η5-C9H7)Ru(C2H4)(PPh3)X] (4, 5) in nearly quantitative yields. Treatment of 2 with AgPF6 and ethene affords [(η5-C9H7)Ru(C2H4)(PPh3)2]PF6 (6), which reacts with acetone to give the substitution product [(η5-C9H7)Ru(OCMe2)(PPh3)2]PF6 (7). The molecular structure of 7 has been determined crystallographically. Whereas treatment of 4 with CH(CO2Et)N2 yields the olefin complex [(η5-C9H7)Ru{η2-(Z)-C2H2(CO2Et)2}(PPh3)Cl] (8), the reactions of 4 and 5 with Ph2CN2, PhCHN2 and (Me3Si)CHN2 lead to the formation of the carbeneruthenium(II) derivatives [(η5-C9H7)Ru(CRR′)(PPh3)Cl] (9-11) and [(η5-C9H7)Ru(CRR′)(PPh3)(κ1-O2CCF3)] (12-14), respectively. Treatment of 9 (R = R′ = Ph), 10 (R = H, R′ = Ph) and 11 (R = H, R′ = SiMe3) with MeLi produces the hydrido(olefin) complexes [(η5-C9H7)RuH(η2-CH2CPh2)(PPh3)] (15), [(η5-C9H7)RuH(η2-CH2CHPh)(PPh3)] (18a,b) and [(η5-C9H7)RuH(η2-CH2CHSiMe3)(PPh3)] (19) via C-C coupling and β-hydride shift. The analogous reactions of 11 with PhLi gives the η3-benzyl compound [(η5-C9H7)Ru{η3-(Me3Si)CHC6H5}(PPh3)] (20). The η3-allyl complex [(η5-C9H7)Ru(η3-1-PhC3H4)(PPh3)] (17) was prepared from 10 and CH2CHMgBr by nucleophilic attack. 相似文献
8.
García-Peñas A Gómez-Ruiz S Pérez-Quintanilla D Paschke R Sierra I Prashar S del Hierro I Kaluđerović GN 《Journal of inorganic biochemistry》2012,106(1):100-110
Titanocene dichloride [Ti(η5-C5H5)2Cl2] (1), has been grafted onto dehydrated hydroxyapatite (HAP), Al2O3 and two mesoporous silicas MSU-2 (Michigan State University Silica type 2) and HMS (Hexagonal Mesoporous Silica), to give the novel materials HAP/[Ti(η5-C5H5)2Cl2] (S1) (1.01 wt.% Ti), Al2O3/[Ti(η5-C5H5)2Cl2] (S2) (2.36 wt.% Ti), HMS/[Ti(η5-C5H5)2Cl2] (S3) (0.75 wt.% Ti) and MSU-2/[Ti(η5-C5H5)2Cl2] (S4) (0.74 wt.% Ti), which have been characterized by powder X-ray diffraction, X-ray fluorescence, nitrogen gas sorption, multinuclear magic angle spinning NMR spectroscopy, IR spectroscopy, thermogravimetry analysis, UV spectroscopy, scanning electronic microscopy and transmission electronic microscopy. The cytotoxicity of the titanocene-functionalized materials toward human cancer cell lines from five different histogenic origins: 8505 C (anaplastic thyroid cancer), A253 (head and neck cancer), A549 (lung carcinoma), A2780 (ovarian cancer) and DLD-1 (colon cancer) has been determined. M50 values (quantity of material needed to inhibit normal cell growth by 50%) and Ti-M50 values (quantity of anchored titanium needed to inhibit normal cell growth by 50%) indicate that the activity of S1-S4 against studied human cancer cells depended on the surface type as well as on the cell line. In addition, studies on the titanocene release and the interaction of the materials S1-S4 with DNA show that the cytotoxic activity may be due to particle action, because no release of titanium complexes has been observed in physiological conditions, while electrostatic interactions of titanocene-functionalized particles with DNA have been observed. 相似文献
9.
The cytotoxic effect of vanadocene dichloride (Cp2VCl2, 1) and its ring-substituted, (η5-C5H4Me)2VCl2 (2), (η5-C5Me5)2VCl2 (3), (η5-C5H4R)2VCl2 (4: R = MeOCH2CH2-, 5: R = 2-MeOC6H4CH2-, 6: R = 4-MeOC6H4CH2-) and ansa-bridged analogs Me2C(η5-C5H4)2VCl2 (7) and Me4C2(η5-C5H4)2VCl2 (8) was investigated. Synthesis of two new methoxy-functionalized compounds (4 and 5) is described. They were characterized by spectroscopic methods and X-ray diffraction analysis. The cytotoxicity studies were performed with leukemic cells MOLT-4. 相似文献
10.
Gómez-Ruiz S Kaluderović GN Prashar S Polo-Cerón D Fajardo M Zizak Z Sabo TJ Juranić ZD 《Journal of inorganic biochemistry》2008,102(8):1558-1570
A variety of substituted titanocene and ansa-titanocene complexes have been synthesized and characterized using traditional methods. The cytotoxic activity of the different titanocene complexes was tested against tumour cell lines human adenocarcinoma HeLa, human myelogenous leukemia K562, human malignant melanoma Fem-x and normal immunocompetent cells, peripheral blood mononuclear cells PBMC. Alkenyl substitution, either on the cyclopentadienyl ring or on the silicon-atom ansa-bridge of the titanocene compounds [Ti{Me2Si(η5-C5Me4)(η5-C5H3{CMe2CH2CH2CHCH2})}Cl2] (8), [Ti{Me(CH2CH)Si(η5-C5Me4)(η5-C5H4)}Cl2] (9) and [Ti(η5-C5H4{CMe2CH2CH2CHCH2})2Cl2] (12) showed higher cytotoxic activities (IC50 values from 24 ± 3 to 151 ± 10 μM) relative to complexes bearing an additional alkenyl-substituted silyl substituent on the silicon bridge [Ti{Me{(CH2CH)Me2SiCH2CH2}Si(η5-C5Me4)(η5-C5H4)}Cl2] (10) and [Ti{Me{(CH2CH)3SiCH2CH2}Si(η5-C5Me4)(η5-C5H4)}Cl2] (11) which causes a dramatic decrease of the cytotoxicity (IC50 values from 155 ± 9 to >200 μM). In addition, the synthesis of the analogous niobocene complex [Nb(η5-C5H4{CMe2CH2CH2CH=CH2})2Cl2] (13), is described. Structural studies based on DFT calculations of the most active complexes 8, 9 and 12 and the X-ray crystal structure of 13 are reported. 相似文献
11.
Complexes of the type (η4-BuC5H5)Fe(CO)2(P) (P = PPh2Py 3, PPhPy24, PPy35; Py = 2-pyridyl) were satisfactorily prepared. Upon treatment of 3 with M(CO)3(EtCN)3 (M = Mo, 6a; W, 6b), the pyridyl N-atom could be coordinated to the metal M, which then eliminates a CO ligand from the Fe-centre and induced an oxidative addition of the endo-C-H of (η4-BuC5H5). This results in a bridged hydrido heterodimetallic complex [(η5-BuC5H4)Fe(CO)(μ-P,N-PPh2Py)(μ-H)M(CO)4] (M = Mo, 7a, 81%; W, 7b, 76%). The reaction of 4 or 5 with 6a,b did not give the induced oxidative addition, although these complexes contain more than one pyridyl N-atom. The reaction of 4 with M(CO)4(EtCN)2 (M = Mo, 9a; W, 9b) produced heterodimetallic complexes [(η4-BuC5H5)Fe(CO)2(μ-P:N,N′-PPhPy2)M(CO)4] (M = Mo, 10a, 81%; W, 10b, 83%). Treatment of 5 with 6a,b gave [(η4-BuC5H5)Fe(CO)2(μ-P:N,N′,N″-PPy3)M(CO)3] (M = Mo, 12a, 96%; W, 12b, 78%). 相似文献
12.
Martin A. Bennett Matthew J. Byrnes Guandolina Chung Alison J. Edwards Anthony C. Willis 《Inorganica chimica acta》2005,358(5):1692-1708
Reaction of cis-[Ru(acac)2(η2-C8H14)2] (1) (acac = acetylacetonato) with two equivalents of PiPr3 in THF at −25 °C gives trans-[Ru(acac)2(PiPr3)2], trans-3, which rapidly isomerizes to cis-3 at room temperature. The poorly soluble complex [Ru(acac)2(PCy3)2] (4), which is isolated similarly from cis-[Ru(acac)2(η2-C2H4)2] (2) and PCy3, appears to exist in the cis-configuration in solution according to NMR data, although an X-ray diffraction study of a single crystal shows the presence of trans-4. In benzene or toluene 2 reacts with PiPr3 or PCy3 to give exclusively cis-[Ru(acac)2(η2-C2H4)(L)] [L = PiPr3 (5), PCy3 (6)], whereas in THF species believed to be either square pyramidal [Ru(acac)2L], with apical L, or the corresponding THF adducts, can be detected by 31P NMR spectroscopy. Complexes 3-6 react with CO (1 bar) giving trans-[Ru(acac)2(CO)(L)] [L = PiPr3 (trans-8), PCy3 (trans-9)], which are converted irreversibly into the cis-isomers in refluxing benzene. Complex 5 scavenges traces of dinitrogen from industrial grade dihydrogen giving a bridging dinitrogen complex, cis-[{Ru(acac)2(PiPr3)} 2(μ-N2)] (10). The structures of cis-3, trans-4, 5, 6 and 10 · C6H14 have been determined by single-crystal X-ray diffraction. Complexes trans- and cis-3, 5, 6, cis-8, and trans- and cis-9 each show fully reversible one-electron oxidation by cyclic voltammetry in CH2Cl2 at −50 °C with E1/2(Ru3+/2+) values spanning −0.14 to +0.92 V (versus Ag/AgCl), whereas for the vinylidene complexes [Ru(acac)2 (CCHR)(PiPr3)] [R = SiMe3 (11), Ph (12)] the process is irreversible at potentials of +0.75 and +0.62 V, respectively. The trend in potentials reflects the order of expected π-acceptor ability of the ligands: PiPr3, PCy3 <C 2H4 < CCHR < CO. The UV-Vis spectrum of the thermally unstable, electrogenerated RuIII-ethene cation 6+ has been observed at −50 °C. Cyclic voltammetry of the μ-dinitrogen complex 10 shows two, fully reversible processes in CH2Cl2 at −50 °C at +0.30 and +0.90 V (versus Ag/AgCl) corresponding to the formation of 10+ (RuII,III) and 102+ (RuIII,III). The former, generated electrochemically at −50 °C, shows a band in the near IR at ca. 8900 cm−1 (w1/2 ca. 3700 cm−1) consistent with the presence of a valence delocalized system. The comproportionation constant for the equilibrium 10 + 102+ ? 2 10+ at 223 K is estimated as 1013.6. 相似文献
13.
Keisham Sarjit Singh Volodymyr Svitlyk Yurij Mozharivskyj 《Inorganica chimica acta》2009,362(15):5252-1023
A series of water soluble compounds of general formula [{(η6-arene)Ru(HMP)Cl}], [η6-arene = η6-cymene (1), η6-HMB (2), η6-C6H6 (3); HMP = 5-hydroxy-2-(hydroxymethyl)-4-pyrone] have been prepared by the reaction of [{(η6-arene) RuCl2}2] with HMP. The complexes 1 and 2 react with NaN3 to give in excellent yield tetra-azido complexes [{(η6-arene)Ru(μN3)N3}2] (arene = cymene 4, HMB = 5) but similar reaction of complex 3 with NaN3 yielded di-azdo complex [{(η6-C6H6)Ru(μN3)Cl}2] (6). Reaction of [{(η6-arene)Ru(μN3)Cl}2] with HMP in the presence of NaOMe resulted in the formation of azido complex [{(η6-arene)Ru(HMP)N3}]. Mono and dinuclear complexes [{(η6-arene)Ru(HMP)(L1)}]+ and [{(η6-arene)Ru(HMP)}2(μL2)]2+ were also prepared by the reaction of complexes 1 and 2 with the appropriate ligand, L1 or L2 in the presence of AgBF4 (L1 = PyCN, DMAP; L2 = 4,4′-bipy, pyrazine). The complexes are characterized on the basis of spectroscopic data and molecular structures of three representative compounds have been determined by single crystal X-ray diffraction study. 相似文献
14.
Rosa Fandos Antonio Otero Ana Rodríguez Sara Suizo Pilar Terreros 《Inorganica chimica acta》2011,366(1):122-127
The reaction of [TiCp*Cl3] with [Fe(η5-C5H5)(η5-C5H4COOH)] in the presence of NEt3 yields [TiCp*{(OOC-C5H4)FeCp}3] (1), (Cp = η5-C5H5). The alkyl complex [TiCp*Me3] reacts with [FeCp(η5-C5H4-CH2COOH)] or anthranilic acid rendering the tris-carboxylate titanium complexes [TiCp*{(OOCCH2-C5H4)FeCp}3] (2) and [TiCp*{(OOCC6H4NH2)3] (3), respectively. Complex 3 can be protonated with triflic acid to render [TiCp*{(OOCC6H4NH2)3].HOTf (4). The reaction of [TiCp*Me3] with anthranilic acid in a 1:2 M ratio yields the alkyl carboxylate derivative [TiCp*Me{(OOCC6H4NH2)2] (5). Complex 5 reacts with tBuNC to render the iminoacyl complex [TiCp*(η2-MeCNtBu){(OOCC6H4NH2)2] (6). The reaction of [TiCp*Cl3] with the ferroceneacetic acid, gives [TiCp*Cl2{(OOCCH2-C5H4)FeCp}] (7). The [TiCp*Cl]2(μ-O)[(ΟΟC-C5H4)2Fe] (8) can be obtained by reaction of [TiCp*Cl3] with [Fe(η5-C5H4-COOH)2] in the presence of a base. The molecular structures of 1 and 8 have been established by X-ray diffraction methods. 相似文献
15.
2,5-Diferrocenyl-1,3,4-thiadiazole, 2,5-Fc2-cC2N2S, (3) has been synthesized by a two-fold Negishi ferrocenylation of dibromothiadiazole (1) with FcZnCl (2) (Fc = Fe(η5-C5H4)(η5-C5H5)) in presence of [Pd(Ph3P)4] as catalyst. Additional spacer units between the ferrocenyls and the cC2N2S core could be introduced by using the Sonogashira C,C cross-coupling protocol. Reaction of 2,5-Br2-cC2N2S (1) or 2,5-(C6H4-4′-I)2-cC2N2S (6) with FcCCH (4) using [PdCl2(Ph3P)2] and [CuI] as catalyst produced the appropriate organometallics 2,5-(FcCC)2-cC2N2S (5) or 2,5-(C6H4-4′-CCFc)2-cC2N2S (7). The electronic and structural properties of 3, 5, and 7 were investigated with UV-Vis spectroscopy and single crystal X-ray diffraction (3). Complex 3 adopts a solid state structure with none of the ferrocenyl substituents being coplanar with the thiadiazole ring. Cyclic, square wave, linear sweep voltammetry and in-situ NIR spectro-electrochemistry highlight the electrochemical properties of 3. In dichloromethane (0.1 mol L−1 [N(nBu)4][B(C6F5)4]), compound 3 displays two well resolved electrochemical reversible one-electron events with formal reduction potentials of 0.192 and 0.338 V versus FcH/FcH+. In contrast, in presence of [N(nBu)4][PF6], the thiadiazoles 3 (E0 = 0.22 V), 5 (E0 = 0.18 V) and 7 (E0 = 0.09 V) show simultaneously oxidation of the two ferrocenyl termini versus FcH/FcH+. Spectro-electrochemical studies, performed in a dichloromethane solution of 0.2 mol L−1 [N(nBu)4][B(C6F5)4], also show that 3 can successively be oxidized via 3+ to 32+. A weak IVCT absorption (ε ca. 300 L mol−1 cm−1) at 1560 nm was found and is consistent with appreciable interactions between neutral ferrocenyl and positively charged ferrocenium mixed valent intermediates. Mixed-valent compound 3+ corresponds to a class II molecule according to Robin and Day. 相似文献
16.
One-dimensional lanthanide-ferrocenesuccinate polymeric complexes [M(η2-FcCOC2H4COO)(μ2-η2-FcCOC2H4COO)2(H2O)2]n (Fc = (η5-C5H4)Fe(η5-C5H4), M = Pr, 1; Ce, 2; La, 3) have been synthesized and structurally characterized by single-crystal X-ray crystallography. The three polymers are isomorphous, in which each Ln(III) ion is 10-coordinated and connects with two water molecules and eight oxygen atoms from ferrocenesuccinate units in two kinds of coordination modes: bidentate-chelating mode and tridentate-bridging mode. The variable-temperature magnetic susceptibility in the temperature range 5-300 K for 1 and 2 shows that both of them display weak antiferromagnetic interaction. In addition, the redox and fluorescent properties have been investigated. The redox properties are different from the previous results of transition metal compounds containing ferrocenyl systems. Compared with sodium ferrocenesuccinate, polymers 1 and 3, the fluorescent intensities of 2 are markedly enhanced in the solid state. 相似文献
17.
Heinrich Lang Noelia Mansilla Ron Claus Tobias Rüffer Gerd Rheinwald 《Inorganica chimica acta》2011,373(1):93-99
Individual synthetic routes to heterobimetallic Ti(IV)-Ag(I) acetylides of type {[Ti](μ-σ,π-CCR1)2}AgCCR2 ([Ti] = (η5-C5H4SiMe3)2Ti: R1 = SiMe3: 6, R2 = SiMe3; 7, R2 = Ph. R1 = tBu: 8, R2 = SiMe3; 9, R2 = Ph. [Ti] = (η5-C5H5)2Ti): 10, R1 = tBu, R2 = SiMe3) including (i) the reaction of {[Ti](μ-σ, π-CCR1)2}AgNO3 ([Ti] = (η5-C5H4SiMe3)2Ti): 1, R1 = SiMe3; 2, R1 = tBu. [Ti] = (η5-C5H5)2Ti: 3, R1 = tBu) with LiCCR2 (4, R2 = SiMe3; 5, R2 = Ph) and (ii) treatment of [Ti](CCSiMe3)2 ([Ti] = (η5-C5H4SiMe3)2Ti) (11) with [AgCCR2] (12, R2 = SiMe3; 13, R2 = Ph) are described. The reactions of 1-3 with 4 or 5 appeared to be sensitive towards stoichiometry because an excess of 4 or 5 resulted in the formation of [(Ag(CCR2)2)Li(OEt2)]n (14) and [Ti](CCR1)2. Coordination polymer 14 is also accessible, when, for example, [AgCCSiMe3] (12) is treated with 1 eq. of LiCCSiMe3 (4) in diethyl ether.The titanium(IV)-silver(I) acetylides 6-10 are stable in the dark and at low temperature, while on exposure to light and on heating they decompose to give R2CC-CCR2 together with [Ti](CCR1)2 and elemental silver.Complexes 6-10 contain a mono-nuclear AgCCR2 entity stabilized by the chelate-bonded organometallic π-tweezer molecule [Ti](CCSiMe3)2, which was evinced by structure determination of 7 in the solid state. In 14 linear [Me3SiCC-Ag-CCSiMe3]− units are connected by [Li(OEt2)]+ building blocks forming a coordination polymer. 相似文献
18.
Shishir Ghosh Noorjahan Begum Sergey V. Lindeman Tasneem A. Siddiquee Ebbe Nordlander 《Inorganica chimica acta》2009,362(15):5175-644
Addition of phenyldi(2-thienyl)phosphine (PPhTh2) to [Re2(CO)10−n(NCMe)n] (n = 1, 2) affords the substitution products [Re2(CO)10−n(PhPTh2)n] (1, 2) together with small amounts of fac-[ClRe(CO)3(PPhTh2)2] (3) (n = 2). Reaction of [Re2(CO)10] with PPhTh2 in refluxing xylene affords a mixture which includes 2, [Re2(CO)7(PPhTh2)(μ-PPhTh)(μ-H)] (4), [Re2(CO)7(PPhTh2)(μ-PPhTh)(μ-η1,κ1(S)-C4H3S)] (5) and mer-[HRe(CO)3(PPhTh2)2] (6). Phosphido-bridged 4 and 5 are formed by the carbon-phosphorus bond cleavage of the coordinated PPhTh2 ligand, the cleaved thienyl group being retained in the latter. Reaction of [Mn2(CO)10] with PPhTh2 in refluxing toluene affords [Mn2(CO)9(PPhTh2)] (7) and the carbon-phosphorus bond cleavage products [Mn2(CO)6(μ-PPhTh)(μ-η1,η5-C4H3S)] (8) and [Mn2(CO)5(PPhTh2)(μ-PPhTh)(μ-η1,η5-C4H3S)] (9). Both 8 and 9 contain a bridging thienyl ligand which is bonded to one manganese atom in a η5-fashion. 相似文献
19.
Dmitry A. Loginov 《Inorganica chimica acta》2008,361(6):1715-1721
The B-phenylborole complex CpRh(η5-C4H4BPh) (1) reacts with [ML]+ fragments to give the arene-type cationic complexes [CpRh(μ-η5:η6-C4H4BPh)ML]+ (ML = RuCp∗ (3), Co(C4Me4) (4), Rh(cod) (5), and Ir(cod) (6)). Cation 4 undergoes a reversible rearrangement into the triple-decker complex [CpRh(μ-η5:η5-C4H4BPh)Co(C4Me4)]+ (7) under visible light irradiation in CH2Cl2 solution. DFT calculations revealed greater stability of arene-type complexes over triple-decker isomers. The structure of [3]BF4 was determined by X-ray diffraction. 相似文献
20.
The dinuclear complex [(η6-C6H6)Ru(μ-N3)Cl]2 (1) is obtained by the reaction of [(η6-C6H6)RuCl2]2 with sodium azide in ethanol. The benzene ruthenium β-diketonato complexes of the general formula [(η6-C6H6)Ru(L∩L)Cl] {L∩L = O,O′-acac (2); O,O′-bzac (3); O,O′-dbzm (4)} are obtained in methanol by the reaction of [(η6-C6H6)RuCl2]2 with the corresponding β-diketonates. These complexes further react with sodium azide in ethanol to yield complexes of the type [(η6-C6H6)Ru(L∩L)N3] [L∩L = O,O′-acac (5); L∩L = O,O′-bzac (6); L∩L = O,O′-dbzm (7)]. The complexes 5-7 are obtained as well by treating 1 with sodium salts of β-diketonates. These neutral benzene ruthenium azido complexes undergo [3+2] dipolar cycloaddition reaction with activated alkynes (MeO2CCCCO2Me, EtO2CCCCO2Et) or fumaronitrile (NCHCCHCN) to yield the corresponding benzene ruthenium triazolato complexes; [(η6-C6H6)Ru(O,O′-acac){N3C2(CO2Me)2}] (8), [(η6-C6H6)Ru(O,O′-acac){N3C2(CO2Et)2}] (9), [(η6-C6H6)Ru(O,O′-acac){N3C2HCN}] (10), [(η6-C6H6)Ru(O,O′-bzac){N3C2HCN}] (11) and [(η6-C6H6)Ru(O,O′-dbzm){N3C2HCN}] (12). These complexes are fully characterized on the basis of microanalyses, FT-IR and FT-NMR spectroscopy. The molecular structure of [(η6-C6H6)Ru(O,O′- acac){N3C2(CO2C2H5)2}] (9) is confirmed by single crystal X-ray diffraction study. 相似文献