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1.
[H(DMSO) 2][ trans-RuCl 4(DMSO) 2] (1) reacts with 2,2′-bipyridine in ethanol at room temperature resulting in the formation of a major compound, mer-[RuCl 3(DMSO)(bpy)] (bpy = 2,2′-bipyridine) 3 and a known minor compound, cis-[RuCl 2(DMSO) 4] (4). The compounds 3 and 4 are formed via an anticipated intermediate mer-[RuCl 3(DMSO) 3] (2). The reaction of 3 and mer-[RuCl 3(TMSO)(bpy)] (5) with small molecules like imidazole, carbon monoxide and KSCN yield, mer-[RuCl 3(bpy)(im)] · 2DMSO (im = imidazole) (6) and cis-[RuCl 2(TMSO)(CO)(bpy)] (7), cis-[RuCl 2(DMSO)(CO)(bpy)] (8) and K[RuCl 3(bpy)(SCN)] (9), respectively. The formations of 3, 6 and 7 have been authenticated by single crystal structure determinations. Compound 6 is formed by the substitution of DMSO or TMSO from 3 and 5, respectively, whereas 7 and 8 are formed by unprecedented one-electron reductions of 5 and 3. The reactions of 3 and 5 with KSCN resulted in the same compound, K[RuCl 3(NCS)(bpy)] (9). DFT calculations were performed to distinguish whether the thiocyanate ligand is bound to ruthenium through S or N. In the ruthenium bipyridine systems, the HOMO contains ruthenium d-orbitals and the LUMO is typically π *-orbitals of the bipyridine ring. Complexes 3, 6 and 7 are redox active in acetone and DMSO solvent showing prominent a reduction peak and corresponding oxidation peak. 相似文献
2.
Recently, much attention has been paid to Ru(II) complexes because of their excellent properties of photochemistry, phtophysis. Bis(2,2'-bipyridine)[4-methyl-4'-(6-bromohexyl)-2,2'-bipyridine] ruthenium(II) perchlorate has been used as an active material for electrochemiluminescent (ECL) sensor for selective detection of oxalic acid.It is known that ECL efficiency of Ru(phen) 32+ is much higher than that of Ru(bpy) 32+. In order to make out more efficient ECL sensor, we have designed and synthesized a new Ru(II) complex, Ru(phen) 2[phen-NHCO(CH 2) 4Br](PF 6) 2. 相似文献
3.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
4.
In the reaction of cis-(CO) 4(SnPh 3)Re[C(OEt)NR 2] (R = ipr (isopropyl), chex (cyclohexyl)) with BI 3 the Lewis acid attacks the triphenylstannyl ligand. Substitution of a phenyl for a iodine group leads to equilibrium mixtures of rhenium carbene complexes of general formula cis-(CO) 4(SnPh 3−χI χ)Re[C(OEt)NR 2] (χ = 1−3; R = ipr, chex). By changing the solvent and ratio of can be shifted such that only one major product is formed. Thus this reaction pathway can be used for the preparation of cis-(CO) 4(SnPhI 2)Re[C(OEt)NR 2] (R = ipr, chex). Even when a large excess of BI 3 is present electrophilic attack by the Lewis acid on the carbene ligand is not observed. Synthesis of cis-(CO)4(SnPh3−χIχ)Re[C(OEt)NR2] (χ = 1−3; R --- ipr, chex) can be achieved in high yield by reaction of cis-(CO)4(SnPh3)Re[C(OEt)NR2] (R = ipr, chex) with one, two or three equivalents of HI. This reaction, with successive rupture of the tin-carbon bonds in the triphenylstannyl ligand and the simultaneous formation of benzene, affords the desired substitution product irreversibly. Reaction of cis-(CO)4(SnPh3)Re[C(OEt)NR2] (R = ipr, chex) with I2 gives the compounds, cis-(CO)4(SnI3)Re[C(OEt)NR2] (R = ipr, chex), in relatively low yields. 相似文献
5.
The synthesis of the homoleptic molybdenum imido compound Li 2Mo(NBu t) 4 is reported. The complexes M (NBu t) 2(NHBu t) 2 (M = Mo, W) can be protonated with various strong acids giving neutral species. The X-ray crystal structure of the tungsten complex W (NBu t) 2(NH 2Bu t) 2 (SO 3CF 3) 2 confirms the presence of O-coordinated cis- CF 3SO 3 groups. 相似文献
6.
Reaction of Ru(PPh 3) 2Br 2 with the NNS chelating tridentate ligand 2-pyridyl- N-(2′-methylthiophenyl)methyleneimine (L) led to the isolation of the ruthenium(II) complex [Ru(L)(PPh 3)Br 2]. Reactivity of this complex with different bidentate chelating ligands revealed that the products are quite different from those obtained by reacting Ru(L)(PPh 3)Cl 2 (the corresponding cis dichloro complex) with the same ligands under comparable conditions. The mixed chelates were isolated and characterised by elemental analysis, magnetic moment measurement and by different spectroscopic methods along with their precursor. Electrochemistry of the complexes was examined by cyclic voltammetry using a platinum working electrode and a Ag/AgCl electrode as reference. The crystal structure of [Ru(L)(PPh 3)Br 2] disclosed that, unlike Ru(L)(PPh 3)Cl 2, the two bromo ligands are in trans position and this explained the difference in its reactivity pattern from the corresponding chloro complex. 相似文献
7.
The complexes [Ru(S,S) 2(PPh 3) 2] [S,S = EtCOCS 2−, (CH 2) 4NCS 2−] react with a variety of tertiary phosphines with the substitution of triphenylphosphine and the formation of [Ru(S,S) 2(PR 3) 2]. The reaction occurs with the formation ofthe cis isomer, except for the complex with PMe 2Ph that gives rise to the trans isomer as the crystal structure shows. The effect of the different phosphines on the ruthenium complex is analysed in terms of the spectroscopic and electrochemical properties of the isolated compounds. The cyclic voltammetric studies of the cis complexes show that isomerization to the trans isomer occurs on oxidation. This isomerization is not observed in the trans-[Ru(S,S) 2(PMe 2Ph) 2] complexes that give rise to stable trans-ruthenium(II)/ruthenium(III) couples. In a similar way the diphosphine complexes afford a quasi-reversible cis-ruthenium(II)/ruthenium(III) process. 相似文献
8.
[Re 2(Ala) 4(H 2O) 8](ClO 4) 6 (Re=Eu, Er; Ala=alanine) were synthesized, and the low-temperature heat capacities of the two complexes were measured with a high-precision adiabatic calorimeter over the temperature range from 80 to 370 K. For [Eu 2(Ala) 4(H 2O) 8](ClO 4) 6, two solid–solid phase transitions were found, one in the temperature range from 234.403 to 249.960 K, with peak temperature 243.050 K, the other in the range from 249.960 to 278.881 K, with peak temperature 270.155 K. For [Er 2(Ala) 4(H 2O) 8](ClO 4) 6, one solid–solid phase transition was observed in the range from 270.696 to 282.156 K, with peak temperature 278.970 K. The molar enthalpy increments, Δ Hm, and entropy increments,Δ Sm, of these phase transitions, were determined to be 455.6 J mol −1, 1.87 J K −1 mol −1 at 243.050 K; 2277 J mol −1, 8.43 J K −1 mol −1 at 270.155 K for [Eu 2(Ala) 4(H 2O) 8](ClO 4) 6; and 4442 J mol −1, 15.92 J K −1 mol −1 at 278.970 K for [Er 2(Ala) 4(H 2O) 8](ClO 4) 6. Thermal decompositions of the two complexes were investigated by use of the thermogravimetric (TG) analysis. A possible mechanism for the thermal decomposition is suggested. 相似文献
9.
Treatment of ruthenium complexes [CpRu(AN) 3][PF 6] (1a) (AN=acetonitrile) with iron complexes CpFe(CO) 2X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe 3, PMe 2Ph, PMePh 2, PPh 3, P(OPh) 3; X=Cl, Br, I) in refluxing CH 2Cl 2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO) 2X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe 3, PMe 2Ph, PMePh 2, PPh 3, P(OPh) 3; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN) 2][PF 6] (1b: L=CO, 1c: P(OMe) 3) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)] 2 was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH 2Cl 2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe 3. 相似文献
10.
The complexation behaviour of cis- und trans-3-diphenylphosphino-4-hydroxyl-tetrahydrofurans with [Rh(COD) 2]BF 4 is studied with the help of NMR and IR spectroscopy. In dependence of the spatial arrangement of hydroxyl and phosphino group the formation of different intra- and intermolecular bridged O-P complexes has been observed. ZusammenfassungDas Komplexierungsverhalten von cis- und trans-3-Diphenylphosphino-4-hydroxy-tetrahydrofuranen mit [Rh(COD)2]BF4 wird mit Hilfe von NMR- und IR-Spektroskopie studiert. In Abhängigkeit von der räumlichen Anordnung von Hydroxy- und Phosphinogruppe zueinander wird die Bildung von intra- bzw. intermolekular verbrückten O-P-Komplexen beobachtet. 相似文献
11.
Two polymeric mercury(II) halide adducts of an olefinic double betaine, cis-( p-Me 2NC 5H 4N +) 2C 2(COO −) 2 (L), have been prepared and characterized by X-ray crystallography. [{Hg 2L 2Cl 4·6HgCl 2} n] (1) crystallizes in the monoclinic space group C2/ c with Z = 4, and [{Hg 2L 2Br 4·HgBr 2} n] (2) in the triclinic space group P
with Z = 1. Complexes 1 and 2 are structurally similar, being composed of centrosymmetric fourteen-membered rings and nearly linear HgX 2 (X = Cl, Br) moieties that are further inter-linked by weak HgX [HgCl = 2.930–3.136(9) Å, HgBr = 3.057–3.310(6) Å] and HgO [2.64, 2.75(3) Å] bonds to generate a two-dimensional polymeric network. 相似文献
12.
The reactions of the diruthenium carbonyl complexes [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)]X (X=BF 4− (1a) or PF 6− (1b)) with neutral or anionic bidentate ligands (L,L) afford a series of the diruthenium bridging carbonyl complexes [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-(L,L)) 2]X n ((L,L)=acetate (O 2CMe), 2,2′-bipyridine (bpy), acetylacetonate (acac), 8-quinolinolate (quin); n=0, 1, 2). Apparently with coordination of the bidentate ligands, the bound acetate ligand of [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)] + either migrates within the same complex or into a different one, or is simply replaced. The reaction of [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)] + (1) with 2,2′-bipyridine produces [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe) 2] (2), [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe)(η 2-bpy)] + (3), and [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-bpy) 2] 2+ (4). Alternatively compound 2 can be prepared from the reaction of 1a with MeCO 2H–Et 3N, while compound 4 can be obtained from the reaction of 3 with bpy. The reaction of 1b with acetylacetone–Et 3N produces [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe)(η 2-acac)] (5) and [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-acac) 2] (6). Compound 2 can also react with acetylacetone–Et 3N to produce 6. Surprisingly [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-quin) 2] (7) was obtained stereospecifically as the only one product from the reaction of 1b with 8-quinolinol–Et 3N. The structure of 7 has been established by X-ray crystallography and found to adopt a cis geometry. Further, the stereospecific reaction is probably caused by the second-sphere π–π face-to-face stacking interactions between the phenyl rings of dppm and the electron-deficient six-membered ring moiety of the bound quinolinate (i.e. the N-included six-membered ring) in 7. The presence of such interactions is indeed supported by an observed charge-transfer band in a UV–vis spectrum. 相似文献
13.
The reaction of Cp(dppe)FeI with the ligands 2,2′- and 4,4′-dithiobispyridine (S 2(Py) 2) give the mononuclear or binuclear complexes of the type [Cp(dppe)Fe-S 2(Py) 2]PF 6, [Cp(dppe)Fe---SPy]PF 6 or [{Cp(dppe)Fe} 2-μ-SPy](PF 6) 2 depending on the reaction condition. Reaction of Cp(dppe)FeI with dithiobispyridines in presence of TlPF 6 as halide abstractor and using CH 2Cl 2 as a solvent gives the complexes [Cp(dppe)Fe-4,4′-S 2(Py) 2) 2]PF 6 (1) and [CpFe(dppe)-2,2′-S 2(Py) 2]PF 6 (2) whereas the same reaction using CH 3OH as a solvent and NH 4PF 6 as the halide abstractor leads to the formation of the Fe III–thiolate complex [Cp(dppe)Fe-2,2′-SPy]PF 6 (3) and the mixed-valence complex [Cp(dppe)Fe III-μSPy-Fe II(dppe)Cp](PF 6) 2 (4). Magnetic and ESR measurements are in agreement with one unpaired electron delocalized between them. Mössbauer data indicate clearly the presence of two different iron sites, each one of the N-bonded and S-bonded iron atoms, with intermediate oxidation state Fe II---Fe III. An electron transfer intervalence absorption was observed for this complex at 780 nm (in CH 2Cl 2). By applying the Hush theory the intervalence parameters were obtained; =0.028, Hab=361 cm −1 which indicate Class II Robin–Day. Estimation of the rate electron transfer affords a value kth=6.5×10 6 s −1. Solvent effect on the intervalence transition follow the Hush prediction for high dielectric constants solvents which permit the evaluation of the outer and inner-sphere reorganizational parameters, which were analyzed and discussed. The electronic interaction parameters compare well with those found for electron transfer in metalloproteins. 相似文献
14.
Reaction of the activated mixture of Re 2(CO) 10, Me 3NO and MeOH with a 1:1 mixture of rac ( d/ l)- and meso-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane (hptpd) yields a mixture of ( d/ l)- and meso-[{Re 2(μ-OMe) 2(CO) 6} 2(μ,μ′-hptpd)] 1. The diastereomers can be easily separated by selective dissolution of d/ l-1 in benzene, and give clearly distinguishable 1H- and 31P-NMR spectra. The fluxional behavior of d/ l-1 in solution has been studied by variable-temperature 1H- and 31P-{ 1H}-NMR spectroscopy. The crystal structures of both d/ l- and meso-1 have been determined. Both molecules consist of two {Re 2(μ-OMe) 2(CO) 6} moieties which are bridged by the two P---CH 2---CH 2---P moieties of the hptpd ligand. Whilst the molecules of meso-1 possess crystallographic i-symmetry, those of d/ l-1 do not have any crystallographic symmetry. These diastereomers therefore give clearly distinguishable Raman spectra in the solid state. Reaction of tris[2-(diphenylphosphino)ethyl]phosphine (tdppep) with the activated mixture affords the complex [{Re 2(μ-OMe) 2(CO) 6}(μ,η 2-tdppep)] 2, and the analogous reaction involving bis[2-diphenylphospinoethyl)phenylphosphine (triphos) gives [{Re 2(μ-OMe) 2(CO) 6}(μ,μ′,η 3-triphos){Re 2(CO) 9}] 3 and [{Re 2(μ-OMe) 2(CO) 6}(μ,η 2-triphos)] 4. 相似文献
15.
The cationic diphenylphosphido-bridged compound [Ru 2(μ-PPh 2)(μ-OH) 2(η 6- p-cymene) 2][PF 6) (2) has been prepared by reaction of the tri-μ-hydroxo complex [Ru 2(μ-OH) 3(η- p-cymene) 2][PF 6] (1) with diphenylphosphine. Complex 2 eliminates water on reaction with protic acids, incorporating the conjugate base of the added acid as a bridging ligand. Formic acid, acetic acid, phenol, and aniline react with 2 to give the monosubstituted compounds [Ru 2(μ-PPh 2)(μ-OH)(μ-L)(η 6- p-cymene) 2]PF 6] (L = HCO 2, MeCO 2, OPh, or NHPH), whereas methanol, thiophenol, 1,2-benzenedithiol, hydrochloric acid and isopropanol afford the disubstituted derivatives [Ru 2(μ-PPh 2)(μ-L) 2(η 6- p-cymene) 2]PF 6] (L = OMe, SPh,
S 2C 6H 4, Cl, or H). 相似文献
16.
The reaction of [ R-( R, R)]-(+) 589-[(η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}Fe(NCMe)]PF 6 with (±)-AsHMePh in boiling methanol yields crystalline [ R-[( R)-( R, R)]-(+) 589)-[(η5-C5H5){1,2-C6H4(PMePh)2}Fe(AsHMePH)PF 6, optically pure, in ca. 90% yield, in a typical second-order asymmetric transformation. This complex contains the first resolved secondary arsine. Deprotonation of the secondary arsine complex with KOBu t at −65°C gives the diastereomerically pure tertiary arsenido-iron complex [ R-[( R),( R, R)]]-[((η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}FeAsMePh] · thf, from which optically pure [ R-[( S),( R, R)]]-(+) 589-[(η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}Fe(AsEtMePh)PF 6 is obtained by reaction with iodoethane. Cyanide displaces ( R)-(−) 589-ethylmethylphenylarsine from the iron complex, thereby effecting the asymmetric synthesis of a tertiary arsine, chiral at arsenic, from (±)-methylphenylarsine and an optically active transition metal auxiliary. 相似文献
17.
Toluene solutions of M 2(NMe 2) 6 (M = Mo, W) react with mesitylene selenol (Ar′SeH) to give M 2(SeAr′) 6 complexes. MO 2(OR) 6 (R = tBu, CH 2tBu) react with excess> 6 fold) Ar′SeH to give Mo 2 (SeAr′) 6, whilst W 2(OR) 6(py) 2 (R = iPr, CH 2tBu) react with excess (> 6 fold) Ar′SeH to give W 2(OR) 2(SeAr′) 4. Reaction of MO 2(OPr i) 6 with Ar′SeH produces Mo 2(OPr i) 2 (SeAr′) 4 which crystallizes in two different space groups. These areneselenato complexes are air-stable and insoluble in common organic solvents. X-ray crystallographic studies revealed that the Mo 2(SeAr′) 6 and W 2(SeAr′) 6 compounds are isostructural in the solid state and adopt ethane-like staggered configurations with the following important structural parameters, M---M (W---W/Mo---Mo) 2.3000(11)/2.2175(13) Å, M---Se 2.430 (av.)/2.440 (av.) Å, M---M---SE 97.0° (av.)°. In the solid state W 2(O iPr) 2(SeAr′) 4 adopts the anti-configuration with crystallographically imposed Ci symmetry and W---W 2.3077(7) Å, W---Se 2.435 (av.) Å, W---O 1.858(6) Å; W---W---SE 100.27(3)°, 93.8(3)° and W---W---O 108.41(17)°. Mo 2(OPr i) 2(SeAr′) 4 crystallizes in both P
and A2/ a space groups in which the molecules are isostructural with each other and the tungsten analogue. Important bond lengths and angles are Mo---Mo 2.180(24) Å, Mo---Se 2.432(av.) Å, Mo---O 1.872(9) Å, Mo---Mo---Se 99.39(9)°, 94.71(8)°, Mo---Mo---O 107.55(28)°. 相似文献
18.
Reaction of [18]aneS 6 with two molar equivalents of [Cu(NCMe) 4](ClO 4) in CH 2Cl 2-MeCN affords the binuclear copper(I) complex [Cu 2([18]aneS 6)(NCMe) 2](ClO 4) 2. The single crystal X-ray structure of the complex shows a centrosymmetric cation with two tetrahedral copper(I) centres each coordinated to three thioether S-donors of [18]aneS 6,Cu---S(1) = 2.3200(15), Cu---S(4) = 2.3415(16), Cu---S(7) = 2.3250(15) Å, and to one MeCN molecule, Cu---N(1) = 1.939(5) Å, to give an overall NS 3-donation at the metal centres. Additionally, S(7′) shows a long-range interaction, Cu …S(7′) = 3.318(2) Å thus distorting the coordination geometry of the metal ion towards trigonal bipyramidal. The metal-metal separation of 4.428(2) Å suggests that there is no significant interaction between the copper centres of the dimer. Reaction of [9]aneS 3 with one molar equivalent of [Cu(NCMe) 4](ClO 4) in refluxing MeCN in the presence of ligands, L, affords the adducts [Cu([9]aneS 3)L] + (L = PPh 3, AsPh 3). The single crystal X-ray structure of the complex [Cu([9]aneS 3)(AsPh 3)](ClO 4) shows tetrahedral AsS 3 coordination at copper(I) with [9]aneS 3 bound facially to the metal centre, Cu---S = 2.303(6), Cu---As = 2.322(4) Å. 相似文献
19.
Reactions of the lithium salts of 3-substituted indenes 1, 2 with ZrCl 4(THF) 2 gave two series of nonbridged bis(1-substituted)indenyl zirconocene dichloride complexes. Fractional recrystallization from THF–petroleum ether furnished the pure racemic and mesomeric isomers of [(η 5-C 9H 6-1-C(R 1)(R 2)--- o-C 6H 4---OCH 3) 2ZrCl 2]· nTHF (R 1=R 2=CH 3, n=1, rac-1a and meso-1b; R 1=CH 3, R 2=C 2H 5; n=0.5 or 0, rac-2a and meso-2b), respectively. Complex 1a was further characterized by X-ray diffraction to have a C2 symmetrically racemic structure, where the six-member rings of the indenyl parts are oriented laterally and two o-CH 3O---C 6H 4---C(CH 3) 2--- substituents are oriented to the open side of the metallocene (Ind: bis-lateral, anti; Substituent: bis-central, syn). The four zirconocene complexes are highly symmetrical in solution as characterized by room temperature 1H-NMR, however 1H– 1H NOESY of meso-1b shows that some of the NOE interactions arise from the two separated indenyl parts of the same molecule, which can only be well explained by taking into account the torsion isomers in solution. 相似文献
20.
The use of classical Werner-type cis-[Co(Cl) 2(tetraamine)] + (tetraamine = cyclen or tren) complexes for their complexation study of biologically relevant ligands has been pursued. These chlorocomplexes are found to be in the chloroaqua/chlorohydroxo forms under the physiological conditions used, their chloride substitution reactivity being dominated by conjugate base pathways, specially when tetraamine = cyclen. Further studies with nucleotides indicate that the substitution processes on cis-[Co(H 2O) 2(tetraamine)] 3+, up to neutral pH, correspond to a simple reaction producing final stable phosphato bound mononucleotide complexes. These complexes are found to be an equilibrium mixture between monodentate O-phosphato and chelate O-phosphato- N-nucleotide forms. No evidence has been found for hydrolytic cleavage of the phosphato-nucleoside bond, as found in other systems with activated phosphates or higher pH values. A full kinetic profile of the process is proposed for the systems in the 2–7 pH range which is the same for chloride, nucleoside and nucleotide substitutions. The results are indicative of an important degree of outer-sphere hydrogen bonding between the cobaltocomplex and the entering biologically relevant ligands, as expected for these processes. 相似文献
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