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1.
The neutral arene ruthenium azido complexes [(η6-p-cymene)Ru(LL)(N3)], [LL = acetylacetonato (acac) (4), benzoylacetonato (bzac) (5) diphenylbenzoyl methane (dbzm) (6)] undergo [3+2] cycloaddition reaction with a series of activated alkynes and fumaronitrile to produce the arene ruthenium triazolato complexes: [(η6-p-cymene)Ru(LL){N3C2(CO2R)2}] [LL = (acac), R = Me (7); LL = (bzac), R = Me (8); LL = (dbzm), R = Me (9); LL = (acac), R = Et (10); LL = (bzac), R = Et (11); LL = (dbzm), R = Et (12) and [(η6-p-cymene)Ru(LL)(N3C2HCN)]; LL = acac (13), bzac (14); dbzm (15). However, cationic azido complexes, [(η6-p-cymene)Ru(dppe)(N3)]+ and [(η6-p-cymene)Ru(dppm)(N3)]+ do not undergo such cycloaddition reactions. The complexes were characterized on the basis of microanalyses, FT-IR and NMR spectroscopic data. Crystal structures of representative complexes were determined by single crystal X-ray diffraction.  相似文献   

2.
Ruthenium complexes [(η5-C5H5)Ru(κ1-P-PPh2Py)(PPh3)Cl] (1) and [(η5-C5H5)Ru(κ2-P-N-PPh2Py)(PPh3)]+ (1a) containing diphenyl-2-pyridylphosphine (PPh2Py) are reported. Coordinated PPh2Py in the complex [(η5-C5H5)Ru(κ1-P-PPh2Py)(PPh3)Cl] (1) exhibits monodentate behavior. In presence of NH4PF6 in methanol at room temperature it afforded chelated complex [(η5-C5H5)Ru(κ2-P,N-PPh2Py)(PPh3)]+ (1a). Further, 1 reacted with various species viz., CH3CN, NaCN, NH4SCN and NaN3 to afford cationic and neutral complexes [(η5-C5H5)Ru(κ1-P-PPh2Py)(PPh3)L]+ and [(η5-C5H5)Ru(κ1-P-PPh2Py)(PPh3)L] [L = CH3CN (1b); CN (1c); N3 (1d) and SCN (1e)] and it’s reaction with N,N-donor chelating ligands dimethylglyoxime (H2dmg) and 1,2-phenylenediamine (pda) gave cationic complexes [(η5-C5H5)Ru(κ1-P-PPh2Py)(κ2-N-N)]PF6 [κ2-N-N = dmg (1f) and pda (1g)]. The complexes 1-1g have been characterized by physicochemical techniques and crystal structures of 1, 1a, 1c, 1e and 1f have been determined by single crystal X-ray analyses. Catalytic potential of the complex 1 has been evaluated in water under aerobic conditions. It was observed that the complex 1 selectively catalyzes reduction of aldehyde into alcohol.  相似文献   

3.
Planar chiral alkenylferrocene phosphanes, viz. (Sp)-[Fe(η5-C5H3-1-PPh2-2-CHCR2)(η5-C5H5)] (R = H, (Sp)-2; Ph, (Sp)-5) and (Sp)-[Fe(η5-C5H3-1-PPh2-2-(E)-CHCHR)(η5-C5H5)] (R = Ph, (Sp)-3; C(O)CH3, (Sp)-6; and CO2CH2CH3, (Sp)-7) have been prepared by alkenylation of (Sp)-2-(diphenylphosphanyl)ferrocenecarboxaldehyde and tested as ligands for enantioselective palladium-catalysed allylic alkylation of 1,3-diphenyprop-2-en-1-yl acetate with dimethyl malonate. All phosphanylalkenes formed active catalysts. However, the induced enantioselectivity was only poor to moderate [12-43% ee after 20 h at room temperature], with the ee’s and configuration of the preferred product strongly depending on the ligand structure. The catalytic results have been related to solution properties (NMR, ESI MS) and the solid-state structural data (X-ray diffraction) of [Pd(η3-1,3-Ph2C3H3){(Sp)-22P}]ClO4 ((Sp)-12), which represent a model of the plausible reaction intermediate.  相似文献   

4.
The reactions of PhSe, PhS and Se2− with N-{2-(chloroethyl)}pyrrolidine result in N-{2-(phenylseleno)ethyl}pyrrolidine (L1), N-{2-(phenylthio)ethyl}pyrrolidine (L2), and bis{2-pyrrolidene-N-yl)ethyl selenide (L3), respectively, which have been explored as ligands. The complexes [PdCl2(L1/L2)] (1/7), [PtCl2(L1/L2)] (2/8), [RuCl(η6-C6H6)(L1/L2)][PF6] (3/9), [RuCl(η6-p-cymene)(L1/L2)][PF6] (4/10), [RuCl(η6-p-cymene)(NH3)2][PF6] (5) and [Ru(η6-p-cymene)(L1)(CH3CN)][PF6]2·CH3CN (6) have been synthesized. The L1-L3 and complexes were found to give characteristic NMR (Proton, Carbon-13 and Se-77). The crystal structures of complexes 1, 3-6, 9 and 10 have been solved. The Pd-Se and Ru-Se bond lengths have been found to be 2.353(2) and 2.480(11)/2.4918(9)/2.4770(5) Å, respectively. The complexes 1 and 7 have been explored for catalytic Heck and Suzuki-Miyaura coupling reactions. The value of TON has been found up to 85 000 with the advantage of catalyst’s stability under ambient conditions. The efficiency of 1 is marginally better than 7. The Ru-complexes 3 and 9 are good for catalytic oxidation of primary and secondary alcohols in CH2Cl2 in the presence of N-methylmorpholine-N-oxide (NMO). The TON value varies between 8.0 × 104 and 9.7 × 104 for this oxidation. The 3 is somewhat more efficient catalyst than 9.  相似文献   

5.
Mononuclear neutral arene ruthenium(II) β-diketonato complexes of the general formula (η6-arene)Ru(LL)Cl [LL = 1-phenyl-3-methyl-4-benzoyl pyrazol-5-one (L1), arene = C6H6 (1), p-iPrC6H4Me (2), C6Me6 (3); arene = p-iPrC6H4Me, LL = 1-benzoylacetone (L3) (8); arene = p-iPrC6H4Me, LL = dibenzoylmethane (L4) (9)] have been synthesized and their subsequent substitution reactions with NaN3 in alcohol at room temperature yielded the corresponding neutral terminal azido complexes (η6-arene)Ru(LL)N3 [LL = 1-phenyl-3-methyl-4-benzoyl pyrazol-5-one (L1), arene = C6H6 (4), p-iPrC6H4Me (6), C6Me6 (7); arene = p-iPrC6H4Me, LL = dibenzoylmethane (L4) (10)] as well as a cationic complex [(η6-p-iPrC6H4Me)Ru(L4) (PPh3)]BF4 (12) with PPh3. The [3 + 2] cycloaddition reaction of selective azido complexes with the activated alkynes dimethyl and diethyl acetylenedicarboxylates produced the arene triazolato complexes [(η6-arene)Ru(LL){N3C2(CO2R)2}] [arene = p-iPrC6H4Me, LL = L1, R = Me (13); arene = C6Me6, LL = L1, R = Me (14); arene = C6Me6, LL = acetyl acetone (L2), R = Me (15); arene = C6Me6, LL = L3, R = Me (16); arene = p-iPrC6H4Me, LL = L1, R = Et (17); arene = C6Me6, LL = L1, R = Et (18); arene = C6Me6, LL = L2, R = Et (19); arene = C6Me6, LL = L3, R = Et (20)]. With fumaronitrile the reaction yielded the triazoles [(η6-arene)Ru(LL)(N3C2HCN)] [arene = p-iPrC6H4Me, LL = L1 (21), arene = C6Me6, LL = L1 (22), arene = C6Me6, LL = L2 (23), arene = C6Me6, LL = L3 (24)]. In the above triazolato complexes only N(2) isomer was obtained. The complexes were characterized on the basis of spectroscopic data. Crystal structure of representatives complexes were determined by single crystal X-ray diffraction.  相似文献   

6.
N-Heterocyclic carbene ligands (NHC) were metalated with Pd(OAc)2 or [Ni(CH3CN)6](BF4)2 by in situ deprotonation of imidazolium salts to give the N-olefin functionalized biscarbene complexes [MX2(NHC)2] 3-7 (3: M = Pd, X = Br, NHC = 1,3-di(3-butenyl)imidazolin-2-ylidene; 4: M = Pd, X = Br, NHC = 1,3-di(4-pentenyl)imidazolin-2-ylidene; 5: M = Pd, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 6: M = Ni, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 7: M = Ni, X = I, NHC = 1-methyl-3-allylimidazolin-2-ylidene). Molecular structure determinations for 4-7 revealed that square-planar complexes with cis (5) or trans (4, 6, 7) coordination geometry at the metal center had been obtained. Reaction of nickelocene with imidazolium bromides afforded the η5-cyclopentadienyl (η5-Cp) monocarbene nickel complexes [NiBr(η5-Cp)(NHC)] 8 and 9 (8: NHC = 1-methyl-3-allylimidazolin-2-ylidene; 9: NHC = 1,3-diallylimidazolin-2-ylidene). The bromine abstraction in complexes 8 and 9 with silver tetrafluoroborate gave complexes [NiBr(η5-Cp)(η3-NHC)] 10 and 11. The X-ray structure analysis of 10 and 11 showed a trigonal-pyramidal coordination geometry at the nickel(II) center and coordination of one N-allyl substituent.  相似文献   

7.
New μ-vinylalkylidene complexes cis-[Fe2{μ-η13-Cγ(R′)Cβ(R″)CαHN(Me)(R)}(μ-CO)(CO)(Cp)2] (R = Me, R′ = R″ = Me, 3a; R = Me, R′ = R″ = Et, 3b; R = Me, R′ = R″ = Ph, 3c; R = CH2Ph, R′ = R″ = Me, 3d; R = CH2Ph, R′ = R″ = COOMe, 3e; R = CH2 Ph, R′ = SiMe3, R″ = Me, 3f) have been obtained b yreacting the corresponding vinyliminium complexes [Fe2{μ-η13-Cγ(R′)Cβ(R″)CαN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (2a-f) with NaBH4. The formation of 3a-f occurs via selective hydride addition at the iminium carbon (Cα) of the precursors 2a-f. By contrast, the vinyliminium cis-[Fe2{μ-η13-Cγ (R′) = Cβ(R″)Cα = N(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (R′ = R″ = COOMe, 4a; R′ = R″ = Me, 4b; R′ = Prn, R″ = Me, 4c; Prn = CH2CH2CH3, Xyl = 2,6-Me2C6H3) undergo H addition at the adjacent Cβ, affording the bis-alkylidene complexes cis-[Fe2{μ-η12-C(R′)C(H)(R″)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], (5a-c). The cis and trans isomers of [Fe2{μ-η13-Cγ(Et)Cβ(Et)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (4d) react differently with NaBH4: the former reacts at Cα yielding cis-[Fe2{μ-η13-Cγ(Et)Cβ(Et)CαHN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], 6a, whereas the hydride attack occurs at Cβ of the latter, leading to the formation of the bis alkylidene trans-[Fe2{μ-η12-C(Et)C(H)(Et)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (5d). The structure of 5d has been determined by an X-ray diffraction study. Other μ-vinylalkylidene complexes cis-[Fe2{μ-η13-Cγ(R′)Cβ(R″)CαHN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], (R′ = R″ = Ph, 6b; R′ = R″ = Me, 6c) have been prepared, and the structure of 6c has been determined by X-ray diffraction. Compound 6b results from treatment of cis-[Fe2{μ-η13-Cγ(Ph)Cβ(Ph)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (4e) with NaBH4, whereas 6c has been obtained by reacting 4b with LiHBEt3. Both cis-4d and trans-4d react with LiHBEt3 affording cis-6a.  相似文献   

8.
The indenyl and pentamethylcyclopentadienyl ruthenium(II) complexes [(η5-L3)Ru(L2)Cl] (L3 = C9H7, L2 = dppe (1a), L2 = dppm (1b); L3 = C5Me5, L2 = dppe (2a); L2 = dppm (2b) (where, dppe = Ph2PCH2CH2PPh2 and dppm = Ph2PCH2PPh2) reacts with NaN3 to yield the azido complexes [(η5-C9H7)Ru(L2)N3], L2 = dppe (3a), dppm (3b) and [(η5-C5Me5)Ru(L2)N3], L2 = dppe (4a), dppm (4b), respectively. The azido complexes undergo [3 + 2] dipolar cycloaddition reaction with dimethylacetylenedicarboxylate to yield triazole complexes [(η5-C9H7)Ru(L2)(N3C2(CO2Me)2)], L2 = dppe (5a), dppm (5b) and [(η5-C5Me5)Ru(L2)(N3C2(CO2Me)2)], L2 = dppe (6a), dppm (6b), respectively. The complexes were fully characterized on the basis of microanalyses, FT-IR and NMR spectroscopy. The crystal structures of the starting complex (1a) and representative complexes 5a, 5b and 6a have been established by single X-ray study.  相似文献   

9.
The complex [(η5-C5H5)Ru(PPh3)2Cl] (1) reacts with several arylazoimidazole (RaaiR′) ligands, viz., 2-(phenylazo)imidazole (Phai-H), 1-methyl-2-(phenylazo)imidazole (Phai-Me), 1-ethyl-2-(phenylazo)imidazole (Phai-Et), 2-(tolylazo)imidazole (Tai-H), 1-methyl-2-(tolylazo)imidazole (Tai-Me) and 1-ethyl-2-(tolylazo)imidazole (Tai-Et), gave complexes of the type [(η5-C5H5)Ru(PPh3)(RaaiR′)]+ {where R, R′ = H (2), R = H, R′ = CH3 (3), R = H, R′ = C2H5 (4), R = CH3, R′ = H (5), R, R′ = CH3 (6), R = CH3, R′ = C2H5 (7)}. The complex [(η5-C9H7)Ru(PPh3)2(CH3CN)]+ (8) undergoes reactions with a series of N,N-donor azo ligands in methanol yielding complexes of the type [(η5-C9H7) Ru(PPh3)(RaaiR′)]+ {where R, R′ = H (9), R = H, R′ = CH3 (10), R = CH3, R′ = H (11), R = CH3, R′ = C2H5 (12)}, respectively. These complexes were characterized by FT IR and FT NMR spectroscopy as well as by analytical data. The molecular structure of the complex [(η5-C5H5)Ru(PPh3)(C6H5-NN-C3H3N2)]+ (2) was established by single crystal X-ray diffraction study.  相似文献   

10.
The reaction of the complex [{(η6-C6Me6)Ru(μ-Cl)Cl}2] 1 with sodium azide ligand gave two new dimers of the composition [{(η6-C6Me6)Ru(μ-N3)(N3)}2] 2 and [{(η6-C6Me6)Ru(μ-N3)Cl}2] 3, depending upon the reaction conditions. Complex 3 with excess of sodium azide in ethanol yielded complex 2. These complexes undergo substitution reactions with monodentate ligands to yield monomeric complexes of the type [(η6-C6Me6)Ru(X)(N3)(L)] {X = N3, Cl, L = PPh3 (4a, 9a); PMe2Ph (4b, 9b); AsPh3 (4c, 9c); X = N3, L = pyrazole (Hpz) (5a); 3-methylpyrazole (3-Hmpz) (5b) and 3,5-dimethyl-pyrazole (3,5-Hdmpz) (5c)}. Complexes 2 and 3 also react with bidentate ligands to give bridging complexes of the type [{(η6-C6Me6)Ru(N3)(X)]2(μ-L)} {X = N3, Cl, L = 1,2-bis(diphenylphosphino)methane (dppm) (6, 10); 1,2-bis(diphenylphosphino)ethane (dppe) (7, 11); 1,2-bis(diphenylphosphino)propane (dppp) (8, 12); X = Cl, L = 4,4-bipyridine (4,4′-bipy) (13)}. These complexes were characterized by FT-IR and FT-NMR spectroscopy as well as by analytical data.The molecular structures of the representative complexes [{(η6-C6Me6)Ru(μ-N3)(N3)}2] 2, [{(η6-C6Me6)Ru(μ-N3)Cl}2] 3,[(η6-C6Me6)Ru(N3)2(PPh3)] 4a and [{(η6-C6Me6)Ru(N3)2}2 (μ-dppm)] 6 were established by single crystal X-ray diffraction studies.  相似文献   

11.
Reactions of 0.5 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 (arene = η6-C6H6, η6-p-iPrC6H4Me) and [(Cp∗)M(μ-Cl)Cl]2 (M = Rh, Ir; Cp∗ = η5-C5Me5) with 4,6-disubstituted pyrazolyl-pyrimidine ligands (L) viz. 4,6-bis(pyrazolyl)pyrimidine (L1), 4,6-bis(3-methyl-pyrazolyl)pyrimidine (L2), 4,6-bis(3,5-dimethyl-pyrazolyl)pyrimidine (L3) lead to the formation of the cationic mononuclear complexes [(η6-C6H6)Ru(L)Cl]+ (L = L1, 1; L2, 2; L3, 3), [(η6-p-iPrC6H4Me)Ru(L)Cl]+ (L = L1, 4; L2, 5; L3, 6), [(Cp∗)Rh(L)Cl]+ (L = L1, 7; L2, 8; L3, 9) and [(Cp∗)Ir(L)Cl]+ (L = L1, 10; L2, 11; L3, 12), while reactions with 1.0 eq. of the dinuclear complexes [(η6-arene)Ru(μ-Cl)Cl]2 and [(Cp∗)M(μ-Cl)Cl]2 give rise to the dicationic dinuclear complexes [{(η6-C6H6)RuCl}2(L)]2+ (L = L1, 13; L2, 14; L3, 15), [{(η6-p-iPrC6H4Me)RuCl}2(L)]2+ (L = L1, 16; L2, 17; L3, 18), [{(Cp∗)RhCl}2(L)]2+ (L = L1, 19; L2, 20; L3, 21) and [{(Cp∗)IrCl}2(L)]2+ (L = L1 22; L2, 23; L3 24). The molecular structures of [3]PF6, [6]PF6, [7]PF6 and [18](PF6)2 have been established by single crystal X-ray structure analysis.  相似文献   

12.
The syntheses and characterization of two novel ferrocene derivatives containing 3,5-diphenylpyrazole units of general formula [1-R-3,5-Ph2-(C3N2)-CH2-Fc] {Fc = (η5-C5H5)Fe(η5-C5H4) and R = H (2) or Me (3)} together with a study of their reactivity with palladium(II) and platinum(II) salts or complexes under different experimental conditions is described. These studies have allowed us to isolate and characterize trans-[Pd{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}2Cl2] (4a) and three different types of heterodimetallic complexes: cis-[M{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] {M = Pd (5a) or Pt (5b)}, the cyclometallated products [M{κ2-C,N-[3-(C6H4)-1-Me-5-Ph-(C3N2)]-CH2-Fc}Cl(L)] with L = PPh3 and M = Pd (6a) or Pt (6b) or L = dmso and M = Pt (8b) and the trans-isomer of [Pt{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] (7b). In compounds 4a, 5a, 5b and 7b, the ligand behaves as a neutral N-donor group; while in 6a, 6b and 8b it acts as a bidentate [C(sp2,phenyl),N(pyrazole)] group. A comparative study of the spectroscopic properties of the compounds, based on NMR, IR and UV-Visible experiments, is also reported.  相似文献   

13.
The preparation of the new ligand 8-(di-tert-butylphosphinooxy)quinoline (1) and the palladium derivatives [PdCl2(1)] (2), [Pd(η3-all)(1)]+ [all = C3H5 (3a), 1-PhC3H4 (3b) and 1,3-Ph2C3H3 (3c)] and [Pd(η2-ol)(1)] [ol = dimethyl fumarate (4a) and fumaronitrile (4b)] is reported. The cationic species 3a-3c have been isolated as salts. The complex 3a(BF4) is obtained either from the reaction of 1 with [Pd(μ-Cl)(η3-C3H5)]2 or from the reaction of ClP(CMe3)2 with [Pd(η3-C3H5)(8-oxyquinoline)], followed in both cases by chloride abstraction with NaBF4. In the complexes, the ligand 1 is P,N chelated to the central metal, as shown by the X-ray structural analysis of 3a(BF4). At 25 °C in solution, 3a(BF4) and 3b(BF4) undergo a fast η3−η1−η3 dynamic process which brings about a syn-anti exchange only for the allylic protons cis to phosphorus, while for 4a and 4b a slow rotation of the olefin around its bond axis to palladium takes place. The complexes 2 and 3a(BF4) are efficient catalyst precursors in the coupling of the phenylboronic acid with aryl bromides and chlorides.  相似文献   

14.
The synthesis and characterization of pyrazole derivatives of general formula [C6H4-4-R-1-{(3,5-Me2-C3N2)-CH2-(η5-C5H4)Fe(η5-C5H5)}] [R = OMe (1a) or H (1b)] with a ferrocenylmethyl substituent are described.The study of the reactivity of compounds 1 with palladium(II) acetate has allowed the isolation of complexes (μ-AcO)2[Pd{κ2-C,N-C6H3-4-R-1-[(3,5-Me2-C3N2)-CH2-(η5-C5H4)Fe(η5-C5H5)]}]2 (2) [R = OMe (2a) or H (2b)] that contain a bidentate [C(sp2, phenyl), N] ligand and a central “Pd(μ-AcO)2Pd” unit.Furthermore, treatment of 2 with LiCl produced complexes (μ-Cl)2[Pd{κ2-C,N-C6H3-4-R-1-[(3,5-Me2-C3N2)-CH2-(η5-C5H4)Fe(η5-C5H5)]}]2 (3) [R = OMe (3a) or H (3b)] that arise from the replacement of the acetato ligands by the Cl.Compounds 2 and 3 also react with PPh3 giving the monomeric complexes [Pd{κ2-C,N-C6H3-4-R-1-[(3,5-Me2-C3N2)-CH2-(η5-C5H4)Fe(η5-C5H5)]}X(PPh3)] {X = AcO and R = OMe (5a) or H (5b) or X = Cl and R = OMe (6a) or H (6b)}, where the phosphine is in a cis-arrangement to the metallated carbon atom. Treatment of 3 with thallium(I) acetylacetonate produced [Pd{κ2-C,N-C6H3-4-R-1-[(3,5-Me2-C3N2)-CH2-(η5-C5H4)Fe(η5-C5H5)]}(acac)] (7) [R = OMe (7a) or H (7b)]. Electrochemical studies of the free ligands and the cyclopalladated complexes are also reported. The dimeric complexes 3 also react with MeO2C-CC-CO2Me (in a 1:4 molar ratio) giving [Pd{(MeO2C-CC-CO2Me)2C6H3-4-R-1-[(3,5-Me2-C3N2)-CH2-(η5-C5H4)Fe(η5-C5H5)]}Cl] (8) [R = OMe (8a) or H (8b)], which arise from the bis(insertion) of the alkyne into the σ{Pd-C(sp2, phenyl)} bond of 3.  相似文献   

15.
The reaction of complex [(η6-C6Me6)Ru(μ-Cl)Cl]2 (1) with sodium azide yielded complexes of the composition [(η6-C6Me6)Ru(μ-N3)(N3)]2 (2) and [(η6-C6Me6)Ru(μ-N3)(Cl)]2 (3), depending upon the reaction conditions. Complex 3 with excess of sodium azide in ethanol yielded complex 2. Complexes 2 and 3 undergo substitution reactions with monodentate ligands such as PPh3, PMe2Ph and AsPh3 to yield monomeric complexes. The structure of complex 2 was determined by X-ray crystallography. All these complexes were characterized by micro analytical data and by FT-IR and FT-NMR spectroscopy. Complex 2 crystallizes in the monoclinic space group P21/n with a = 8.5370(11) Å, b = 16.192(2) Å, c = 10.4535(13) Å and β = 110.877(2)°.  相似文献   

16.
Trimethylstannyl (diphenylphosphino)acetate (1), which is readily accessible from potassium (diphenylphosphino)acetate and trimethylstannyl chloride, may serve as the source of (diphenylphosphino)acetate anion in the preparation of coordination compounds. Thus, the reactions between [M(cod)Cl2] (M = Pd and Pt; cod = η22-cycloocta-1,5-diene) and two equivalents of 1 give [M(Ph2PCH2CO22O,P)2] (2 and 3), while the reaction of [{Pd(μ-Cl)Cl(PFur3)}2] (4; Fur = 2-furyl) with one equivalent of 1 yields [SP-4-3]-[PdCl(Ph2PCH2CO22O,P)(PFur3)] (5). The reactions of 1 with the dimers [{Rh(η5-C5Me5)Cl(μ-Cl)}2] and [{Ru(η6-1,4-MeC6H4(CHMe2))Cl(μ-Cl)}2] (at 1-to-metal ratio 1:1) produce O,P-chelated complexes as well, albeit as stable adducts with the liberated Me3SnCl: [RhCl(η5-C5Me5)(Ph2PCH2CO22O,P)] · Me3SnCl (6) and[RuCl(η6-1,4-MeC6H4(CHMe2))(Ph2PCH2CO22O,P)] · Me3SnCl (8). The related complexes with P-monodentate (diphenylphosphino)acetic acid, [RhCl25-C5Me5)(Ph2PCH2CO2H-κ,P)] (7) and [RuCl26-1,4-MeC6H4(CHMe2))(Ph2PCH2CO2H-κP)] (9), were obtained by bridge splitting in the dimers with the phosphinocarboxylic ligand. All new compounds were characterized by spectral methods and combustion analyses, and the structures of 2 · 3CH2Cl2, 3, 4, 5, 6 and 8 were determined by X-ray crystallography.  相似文献   

17.
The dinuclear dichloro complexes [(η6-arene)2Ru2(μ-Cl)2Cl2] and [(η5-C5Me5)2M2(μ-Cl)2Cl2] react with 2-(pyridine-2-yl)thiazole (pyTz) to afford the cationic complexes [(η6-arene)Ru(pyTz)Cl]+ (arene = C6H61, p-iPrC6H4Me 2 or C6Me63) and [(η5-C5Me5)M(pyTz)Cl]+ (M = Rh 4 or Ir 5), isolated as the chloride salts. The reaction of 2 and 3 with SnCl2 leads to the dinuclear heterometallic trichlorostannyl derivatives [(η6-p-iPrC6H4Me)Ru(pyTz)(SnCl3)]+ (6) and [(η6-C6Me6)Ru(pyTz)(SnCl3)]+ (7), respectively, also isolated as the chloride salts. The molecular structures of 4, 5 and 7 have been established by single-crystal X-ray structure analyses of the corresponding hexafluorophosphate salts. The in vitro anticancer activities of the metal complexes on human ovarian cancer cell lines A2780 and A2780cisR (cisplatin-resistant), as well as their interactions with plasmid DNA and the model protein ubiquitin, have been investigated.  相似文献   

18.
Three copper(II) Schiff-base complexes, [Cu(L1)(H2O)](ClO4) (1), [Cu(L2)] (2) and [Cu(L3)] (3) have been synthesized and characterized [where HL1 = 1-(N-ortho-hydroxy-acetophenimine)-2-methyl-pyridine], H2L2 = N,N′-(2-hydroxy-propane-1,3-diyl)-bis-salicylideneimine and H2L3 = N,N′-(2,2-dimethyl-propane-1,3-diyl)-bis-salicylideneimine]. The structure of complex 1 has been determined by single crystal X-ray diffraction analysis. In complex 1, the copper(II) ion is coordinated to one oxygen atom and two nitrogen atoms of the tridentate Schiff-base ligand, HL1. The fourth coordination site of the central metal ion is occupied by the oxygen atom from a water molecule. All the complexes exhibit high catalytic activity in the oxidation reactions of a variety of olefins with tert-butyl-hydroperoxide in acetonitrile. The catalytic efficacy of the copper(II) complexes towards olefin oxidation reactions has been studied in different solvent media.  相似文献   

19.
The DNA binding of polypyridyl (pp) (η5-C5Me5)RhIII complexes of the types [(η5-C5Me5)RhCl(pp)](CF3SO3) (2-6) (pp = bpy, phen, dpq, dppz, dppn), [(η5-C5Me5)Rh{(Me2N)2CS}(pp)](CF3SO3)2 (7-9) (pp = dpq, dppz, dppn) and [(η5-C5Me5)Rh(L)(pp)](CF3SO3) (10) (L = C6H5S) and (11) (L = C10H7S) has been studied by UV/Vis spectroscopy, circular dichroismus and viscosity measurements. Complexes 3-11 are cytotoxic towards the human MCF-7 breast and HT-29 colon cancer cell lines and exhibit IC50 values in the range 0.56-10.7 μM. Stable intercalative binding into CT-DNA is indicated for the dpq and dppz complexes by large increases ΔTm of 6-12 °C in the DNA thermal denaturation temperature for r = [complex]/[DNA] = 0.1 and by induced CD bands and large viscosity increases. In contrast, significant DNA lengthening is not observed after incubation of the biopolymer with the dppn complexes 2 and 9 at molar ratios of r < 0.08. Pronounced hypochromic shifts for the π-π transitions of the dppn ligands in the range 320-425 nm indicate the possible presence of surface stacking. The in vitro cytotoxicities of the chloro complexes 4-6 and the (Me2N)2CS complexes 7-9 are dependent on the size of the polypyridyl ligand with IC50 values decreasing in the order dpq > dppz > dppn. For instance, IC50 values of 5.3, 1.5 and 0.91 μM were determined for 7-9 against MCF-7 cells. Rapid Cl/H2O exchange leads the formation of aqua dications for 4-6, whose levels of cellular uptake and cytotoxicities are similar to those established for 7-9. Intramolecular interactions between the aromatic thiolate and dppz ligands of 10 and 11 prevent significant DNA intercalation. X-ray structural determinations have been performed for 2-7 and 11.  相似文献   

20.
Treatment of [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(COD) (1) with phosphites, phosphines, amines or N-heterocyclic carbene in THF afforded the COD displacement complexes [η5:σ-Me2C(C5H4)(C2B10H10)]Ru[P(OEt)3]2 (2), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru[PPh2(OEt)]2 (3), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru[NH2CH2CH2Pri]2 (4), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)2 (5), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru (η2-NH2CH2CH2NH2) (6), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru[η2-NH(CH3)CH2CH2NH(CH3)] (7) or [η5:σ-Me2C(C5H4)(C2B10H10)]Ru[NHC]2 (8, NHC = 1,3,4,5-tetramethylimidazol-2-yilidene), respectively. Ruthenium-amine complexes were much more labile than 1. Upon exposure to moisture, 5 was converted into [{η5:σ-Me2C(C5H4)(C2B10H10)}Ru(μ-H2O)]2 (9). Reactions of 5 with PR3 (R = PPh3, Cy), TMEDA (TMEDA = N,N,N′,N′-tetramethylethylenediamine) and CH3CN afforded the corresponding amine replacement products[η5:σ-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)(PPh3) (10), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)(PCy3) (11), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(TMEDA) (12) and [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(NCCH3)2 (13). These results indicated that the steric factor dominated these substitution reactions. The electrochemical studies showed that the electron richness of the Ru atom decreased in the order L2Ru(NHC)2 > L2Ru(amine)2 > L2Ru(NCMe)2 > L2Ru(P)2. All of these complexes were fully characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 2, 3, 5-10, 12 and 13 were further confirmed by single-crystal X-ray analyses.  相似文献   

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