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1.
Pyrolysis of an in-situ generated intermediate, produced in the reaction of [CpMoCl4], 1, (Cp = η5-C5Me5) with [LiBH4·THF], with an excess of difuryl ditelluride in toluene at 90 °C yielded syn and anti isomers of [CpMo(O)(μ-Te)]2 (2, 3) and [Cp2Mo2O2(μ-O)(μ-Te)] (4, 5). In a similar fashion, dibenzyl diselenide yielded syn and anti isomers of [CpMo(O)(μ-Se)]2 (6, 7), along with the known nido-[(CpMo)2B4H8Se2]. Note that in parallel with 2-7, [(CpMo)2B5H9] was isolated as the major product in both cases. Compounds 2-7 have been isolated in modest yield as orange to brown crystalline solids. All the new compounds have been characterized in solution by mass, IR, 1H, 13C, 77Se and 125Te NMR spectroscopy, and the structural types were unequivocally established by crystallographic analysis of 2-4 and 7.  相似文献   

2.
Hydrogenation of cyclohexene with 0.1 mol% of the (nitrosyl)ruthenium catalyst [CpRu(NO)(C6H5)2] (1; Cp = η5-C5(CH3)5) under 1.0 MPa of H2 in water at 90 °C for 13 h afforded cyclohexane in 94% yield. The nitrosyl-bridged dinuclear complex [CpRu(μ2-NO)2RuCp] (2) and the mononuclear cyclohexene complex [CpRu(NO)(η2-C6H10)] (3), which also serve as catalyst precursors, have been obtained from the reaction mixture. X-ray crystallographic analyses of 2 and 3 have revealed that the bridging nitrosyl ligands in 2 form an almost planar Ru2N2 four-membered ring with the Ru–Ru distance of 2.5366(5) Å, whereas the nitrosyl ligand in 3 is linear. On the other hand, a ruthenium complex without a nitrosyl ligand [CpRu(CH3CN)3][OSO2CF3] proved to be less effective for this hydrogenation.  相似文献   

3.
A new route was used to synthesize half-sandwich rhodium complexes containing both N-heterocyclic carbenes (NHC) and carborane ligands. The rhodium carbene complexes CpRh(L)[S2C2(B10H10)] (Cp = pentamethylcyclopentadienyl, L = 1,3-dimethylimidazolin-2-ylidene; 4) can be obtained from the reaction of CpRh(L)Cl2 (2) with Li2S2C2(B10H10) or from the reaction of CpRh[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   

4.
The 16-electron half-sandwich complexes CpRh[E2C2(B10H10)] (E = S, 1a; Se, 1b) react with [Ru(COD)Cl2]x under different conditions to give different types of heterometallic complexes. When the reactions were carried out in THF for 24 h, the binuclear Rh/Ru complexes [CpRh(μ-Cl)2(COD)Ru][E2C2(B10H10)] (E = S, 2a; Se, 2b) bridged by two Cl atoms and the binuclear Rh/Rh complexes (CpRh)2[E2C2(B10H10)] (E = S, 3a; Se, 3b) with direct Rh-Rh bond can be isolated in moderate yields. [Ru(COD)Cl2] fragments in 2a and 2b have inserted into the Rh-E bond. If the [Ru(COD)Cl2]x was reacted with 1a in the presence of K2CO3 in methanol solution, the product [CpRh(COD)]Ru[S2C2(B10H10]] (4a), K[(μ-Cl)(μ-OCH3)Ru(COD)]4 (5a) and 3a were obtained. The B(3)-H activation in complex 4a was found. However, when the reaction between 1b and [Ru(COD)Cl2]x was carried out in excessive NaHCO3, the carborane cage opened products {CpRh[S2C2(B9H10)]}Ru(COD) (6b), {CpRh[S2C2(B9H9)]}Ru(COD)(OCH3) (7b) and 3b were obtained. All complexes were fully characterized by their IR, 1H NMR and elemental analyses. The molecular structures of 2a, 2b, 3b, 4a, 5a, and 7b have been determined by X-ray crystallography.  相似文献   

5.
Two hetero-binuclear complexes [CpCoS2C2(B9H10)][Rh(COD)] (2a) and [CpCoSe2C2(B10H10)][Rh(COD)] (2b) [Cp = η5-pentamethylcyclopentadienyl, COD = cyclo-octa-1,5-diene (C8H12)] were synthesized by the reactions of half-sandwich complexes [CpCoE2C2(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   

6.
Chalcogen-stabilized dimolybdaboranes 3-5 (3: [(CpMo)2B4H5Se(Ph)], 4: [(CpMo)2B4H3Se2(SeCH2Ph)] and 5: [(CpMo)2B3H6(BSR)(μ-η1-SR)] (R = 2,6-(tBu)2-C6H2OH)) have been isolated from the mild pyrolysis of dichalcogenide ligands, RE-E‘R (R = Ph: E = S, E‘ = Se; R = CH2Ph, [2,6-(tBu)2-C6H2OH]: E = E‘ = Se, S) and [(CpMo)2B4H8], 2, an intermediate generated from the reaction of [CpMoCl4] (1) (Cp = η5-C5Me5), with [LiBH4.thf]. The geometry of [(CpMo)2B4H5Se(Ph)] is similar to that of [(CpMo)2B5H9], in which one BH3 unit on the open face is replaced by a triple bridged selenium atom. All the compounds have been characterized in solution by 1H, 11B, 13C NMR and IR spectroscopy and elemental analysis. The structural types were unequivocally established by X-ray crystallographic analysis of compounds 3-5.  相似文献   

7.
Reaction of 3,4-dimethylphospholylthallium (Tl-1) with [CpMCl2]2 (M = Rh, Ir) leads to the formation of the dimeric species [(CpM)2(Me2C4H2P)3]+2 and 3 with bridging μ-η11-phospholyl ligands. The phosphametallocenium sandwich complexes [CpM(Me2C4(SiMe3)2P)]+7 (M = Rh) and 8 (M = Ir) could be obtained from the reaction of [CpMCl2]2 and the 2,5-bis(trimethylsilyl)-1-trimethylstannylphosphole 6, with the bulky trimethylsilyl groups preventing the phosphole from η1- and enforcing a η5-coordination. The structures of phospharhodocenium cation 7 and a byproduct 9 containing a phosphairidocenium moiety could be determined by X-ray diffraction.  相似文献   

8.
Reactions of a sulfido- and thiolato-bridged diiridium complex [(CpIr)2(μ-S)(μ-SCH2CH2CN)2] (Cp = η5-C5Me5) with [(CpMCl)2(μ-Cl)2] (M = Ir, Rh) afforded the sulfido- and thiolato-bridged trinuclear clusters [(CpM)(CpIr)23-S)(μ2-SCH2CH2CN)22-Cl)]Cl (4: M = Ir, 5: M = Rh). Upon treatment with XyNC (Xy = 2,6-Me2C6H3) in the presence of KPF6 at 60 °C, 4 was converted into a mixture of a mononuclear XyNC complex [CpIr(SCH2CH2CN)(CNXy)2][PF6] (6) and a dinuclear XyNC complex [{CpIr(CNXy)}2(μ-S)(μ-SCH2CH2CN)][PF6] (7). On the other hand, reactions of 4 and 5 with methyl propiolate in the presence of KPF6 at 60 °C resulted in the formation of a cyclic trimer of the alkyne 1,3,5-C6H3(COOMe)3 as the sole detectable organic product. The reactions proceeded catalytically with retention of the cluster cores of 4 and 5, whereby the activity of the former was much higher than that of the latter.  相似文献   

9.
Four half-sandwich cobalt complexes, CpCo(2-PyS)2 (2), CpCo(2-PyS)2 · HI (3), CpCo(2-PyS) (4-PyS) (4), (CpCo)2(μ-PhS)2(μ-2-PyS)I (5) [Cp = pentamethylcyclopentadienyl, 2-PyS = 2-pyridinethiolate, 4-PyS = 4-pyridinethiolate, PhS = benzenethiolate] were successfully synthesized by the reactions of 2-pyridinethione, lithium 4-pyridinethiolate and lithium benzenethiolate with CpCo(2-PyS)I (1), respectively. Complexes 2 and 3 have the structures with two 2-pyridinethiolates ligands coordinated to the cobalt atom. Two different pyridinethiolates ligands can be identified in complex 4. The molecular structure of 5 consists of two Cp-Co fragments, which are triply bridged by three sulfur atoms from different ligands. The molecular structures of 3 and 5 were determined by X-ray crystallographic analysis. All the complexes have been well characterized by elemental analysis, NMR and IR spectra.  相似文献   

10.
Complexes M(CCCSiMe3)(CO)2Tp′ (Tp′ = Tp [HB(pz)3], M = Mo 2, W 4; Tp′ = Tp [HB(dmpz)3], M = Mo 3) are obtained from M(CCCSiMe3)(O2CCF3)(CO)2(tmeda) (1) and K[Tp′].Reactions of 2 or 4 with AuCl(PPh3)/K2CO3 in MeOH afforded M{CCCAu(PPh3)}(CO)2Tp′ (M = Mo 5, W 6) containing C3 chains linking the Group 6 metal and gold centres.In turn, the gold complexes react with Co33-CBr)(μ-dppm)(CO)7 to give the C4-bridged {Tp(OC)2M}CCCC{Co3(μ-dppm)(CO)7} (M = Mo 7, W 8), while Mo(CBr)(CO)2Tp and Co33-C(CC)2Au(PPh3)}(μ-dppm)(CO)7 give {Tp(OC)2Mo}C(CC)2C{Co3(μ-dppm)(CO)7} (9) via a phosphine-gold(I) halide elimination reaction. The C3 complexes Tp′(OC)2MCCCRu(dppe)Cp (Tp′ = Tp, M = Mo 10, W 11; Tp′ = Tp, M = Mo 12) were obtained from 2-4 and RuCl(dppe)Cp via KF-induced metalla-desilylation reactions. Reactions between Mo(CBr)(CO)2Tp and Ru{(CC)nAu(PPh3)}(dppe)Cp (n = 2, 3) afforded {Tp(OC)2Mo}C(CC)n{Ru(dppe)Cp} (n = 2 13, 3 14), containing C5 and C7 chains, respectively. Single-crystal X-ray structure determinations of 1, 2, 7, 8, 9 and 12 are reported.  相似文献   

11.
The binuclear half-sandwich iridium complexes {CpIrCl2}2(μ-2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene) (3) and {CpIr[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 [CpIrCl(μ-Cl)]2 or the “pseudo-aromatic” half-sandwich iridium complex CpIr[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   

12.
The syntheses of the compounds [M(Cp)(aeaz)(az)](OTf)2 (4, 5) (M = Rh(III), Ir(III); aeaz = C2H4NC2H4NH2, az = C2H4NH (3)) containing cationic N-(2-aminoethyl)aziridine-N,N′ chelate complexes are described. The bis-aziridine complexes [MCl(Cp)(az)2]Cl (M = Rh (1), M = Ir (2)) react with an excess of the aziridine (az) in the presence of AgO3SCF3 (=AgOTf) via AgCl precipitation and az addition followed by a metal-mediated coupling reaction, to give the compounds [M(Cp)(aeaz)(az)](OTf)2 (4, 5). The new aeaz ligand is formally the dimerisation product of az. Using the same reaction conditions with the analogous, but weaker Lewis acidic ruthenium(II) complex [RuCl(C6Me6)(az)2]Cl (6) an anion exchange reaction yielding [RuCl(C6Me6)(az)2]OTf (8) is observed. After purification, all compounds are fully characterized using IR, FAB-MS, 1H and 13C NMR spectroscopy. The single crystal X-ray structure analysis reveals a distorted octahedral geometry for all complexes.  相似文献   

13.
The novel ruthenium dithiolene complexes [(arene)Ru{S2C2(COOMe)2}] (arene = C6H6 (1a), C6H4(Me)(iPr) (1b), C6Me6 (1c)) were synthesized. The equilibrium between complex 1a and the corresponding dimer [(C6H6)Ru{S2C2(COOMe)2}]2 (1a′) was confirmed in solution. The reaction of complex 1a with dimethyl- or diethylacetylene dicaboxylate gave the alkene-bridged adducts [(C6H6)Ru{S2C2(COOMe)2}{C2(COOR)2}] (R = Me (2a), Et (3a)) as [2 + 2] cycloaddition products formally. The reactions of complex 1a with diazo compounds also gave the alkylidene-bridged adducts [(C6H6)Ru{S2C2(COOMe)2}(CHR)] (R = H (4a), SiMe3 (5a), COOEt (6a)) as [2 + 1] cycloaddition products. The electrochemical behavior of complex 1a was investigated. The reductant of complex 1a was a stable species for several minutes. The oxidant of complex 1a was very unstable; the cation 1a+ formed was immediately converted to the corresponding cationic dimer 1a+. The cationic dimer 1a+ was stable for several minutes, and it was rapidly and quantitatively converted to the neutral complex 1a when it was reduced.  相似文献   

14.
The reactions of tri(bis(ethyl)amino)phosphorus ylide (Et2N)3PCH2 with cyclopentadienyl (Cp) metal (V) tetrachloride CpMCl4 (M = Nb 1; Ta 3) and pentamethylcycopentadienyl (Cp) metal (V) tetrachloride CpMCl4 (M = Nb 2; Ta 4) were investigated. The hexa-coordinate ylide adducts complexes 5 (CpNbCl4(H2CP(NEt2)3)), 6 (CpNbCl4(H2CP(NEt2)3)) and 8 (CpTaCl4(H2CP(NEt2)3)) with pseudo-octahedral geometry were structurally analyzed with X-ray diffraction. Compound 4 (CpTaCl4) reacted with three molar equivalent of phosphorus ylide to form one ionic complex 9 ([H3C-P(NEt2)3][CpTaCl5]) which was also structurally analyzed with X-ray diffraction. The possible formation mechanism of compound 9 has been discussed.  相似文献   

15.
The reaction between 1-boranyl-1,3,5-triaza-7-phosphaadamantane ligand N-B-PTA(BH3) and [CpRhCl(μ-Cl)]2 affords [CpRh{N-B-PTA(BH3)}Cl2] (3) or [CpRh{N-B-PTA(BH3)}2Cl]Cl (5) containing one or two P-bonded boronated PTA ligands. The hydride [CpRh{N-B-PTA(BH3)}H2] (8) was also obtained by reaction of 3 with NaBH4 and alternatively by direct hydroboration of [CpRh(PTA)Cl2] with excess NaBH4. Moderately slow hydrolysis of the N-boranyl rhodium complexes affords dihydrogen, H3BO3 and the corresponding PTA derivatives, including the water-soluble dihydride [CpRh(PTA)H2] (9). Finally, the reaction of 8 with electron poor alkynes gives the alkene complexes [CpRh{N-B-PTA(BH3)}(η2-CH2 = CHR)] (R = Ph, 10; C(O)OEt, 11) as a mixture of rotamers η2-coordinated to rhodium without affecting the N-BH3 moiety. The X-ray crystal structures of 3 and 10 were also obtained and are here discussed.  相似文献   

16.
Reactions of phenylethynyl lithium with substituted cyclopentenones gave the corresponding pendant phenylethynyl substituted cyclopentadienes. Subsequent deprotonation and transmetallation with TiCl4·2THF, ZrCl4, and CpZrCl3 yielded the alkyne-functionalized metallocene complexes [C5Me4(CCPh)]2MCl2 [M = Ti (1), Zr (2)], Cp[C5Me4(CCPh)]ZrCl2 (3), and Cp[C5H2R′2(CCPh)]ZrCl2 [R′ = Me (4), Ph (5)]. These complexes were fully characterized by 1H NMR, 13C NMR, MS spectra, and elemental analysis. The molecular structure of 2 was determined by single crystal X-ray diffraction analysis. Ethylene polymerization was studied with these complexes in the presence of methylaluminoxane (MAO).  相似文献   

17.
The cobalt dithiolene complex with the sulfonylamide-substituted Cp ligand [(C5H4-NHTs)Co{S2C2(COOMe)2}] (1, Ts = p-SO2C6H4Me) reacted with TsOH · H2O to give [(C5H4-NH2)Co{S2C2(COOMe)(H)}] (2), [(C5H4-NHTs)Co(S2C2H2)] (3) and [(C5H4-NHTs)Co{S2C2(COOMe)(H)}] (4). Complex 1 was dissolved in a basic aqueous solution, and the anion reacted with Me2SO4 to form the N-methylated product [{C5H4-N(Me)Ts}Co{S2C2(COOMe)2}] (5); the carboxylic acid complex [{C5H4-N(Me)Ts}Co{S2C2(COOMe)(COOH)}] (6) formed by a base hydrolysis. The X-ray crystal structures of complexes 4-6 and the methylsulfonylamide-substituted Cp complex [(C5H4-NHMs)Co{S2C2(COOMe)2}] (7, Ms = SO2Me) were determined. In the crystal structures of complexes 4 and 7, intermolecular hydrogen bondings of NH?O (ca. 2.1 Å) and NH?S (ca. 3.1 Å) were observed. Complex 6 showed the OH?O intermolecular hydrogen bonding (ca. 1.6 Å) of COOH moiety between two molecules, and these two molecules were assembling each other. Complexes 5 and 6 showed an intramolecular π-π interaction between the aromatic cobaltadithiolene and benzene rings, and complex 5 also has intermolecular π-π interactions between two benzene rings, and between two cobaltadithiolene rings.  相似文献   

18.
Two binuclear complexes [CpM(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 [CpMCl(μ-Cl)]2 (M = Rh, Ir). Four mononuclear complexes CpM(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   

19.
The synthesis, characterization and chemistry of novel η3-allyl metal complexes (M = Ir, Rh) are described. The structures of compounds (C5Me4H)Ir(PPh3)Cl2 (1), (C5Me4H)Ir(PPh3)(η3-1-methylallyl)Br (3a), (C5Me4H)Ir(η4-1,3,5-hexatriene) (8), and (C5Me5)Rh(η3-1-ethylallyl)Br (5d) have been determined by X-ray crystallography. Structural comparisons among these complexes are discussed. It is found that the neutral metal allylic complex [CpIrCl(η3-methylallyl)] (5) ionizes in polar solvents to give [CpIr(η3-methylallyl)]+Cl (6) and reaches equilibrium (5 ? 6) at room temperature. Addition of tertiary phosphine ligands to neutral complexes such as [CpIr(η3-methylallyl)Cl], results in the formation of stable ionic phosphine adducts. Factors such as solvent, length of carbon chain, temperature and light are discussed with respect to the formation, stability and structure of the allyl complexes.  相似文献   

20.
Irradiation of CpRu(CO)2CH3 (1) in C6D6 at room temperature yields CpRu(CO)2C6D5 and CH3D (where Cp = n5-C5Me5). CpRu(CO)2CD3 (2) has also been prepared and similar irradiation in C6H6 yields CpRu(CO)2C6H5 (3) and CD3H. This latter reaction confirms that it is the methyl group bonded to ruthenium that is involved in the C-H activation process and not the methyl groups on the Cp ligand system. The compound CpRu(CO)2C6H5 (3) has been prepared for the first time in good yield by the reaction of CpRu(CO)2Br with NaBPh4. X-ray crystal structures of both CpRu(CO)2CH3 (1) and CpRu(CO)2C6H5 (3) have been determined and the results are reported and discussed.  相似文献   

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