共查询到20条相似文献,搜索用时 10 毫秒
1.
Sülü Mustafa Luigi M. Venanzi Tobias Gerfin Volker Gramlich 《Inorganica chimica acta》1998,270(1-2):499-510
The new tripodal phosphine CH3C{CH2P(m-CF3C6H4)2}3, CF3PPP, was prepared by reacting CH3C(CH2Br)3 with Li+P(m-CF3C6H4)2−, the latter being best obtained by adding Li+NiPr2− to PH(m-CF3C6H4)2. The rhodium complexes [RhCl(CO)(CF3PPP)], [Rh(LL)(CF3PPP)](CF3SO3) (LL = 2 CO or NBD), [RhX3(CF3PPP)], [RhX(MeCN)3(CF3PPP)](CF3SO3)2 (X = H and Cl), [RhCl2(MeCN)(CF3PPP)](CF3SO3) and [Rh(MeCN)3(CF3PPP)](CF3SO3)3 were prepared and characterized. The X-ray crystal structure of [Rh(NBD)(CF3PPP)](CF3SO3) is reported. The lower oxygen sensitivity of the CF3PPP rhodium(I) complexes, relative to the corresponding species with the parent ligand CH3C(CH2PPh2)3, is attributed to the higher effective nuclear charge on the metal centers caused by the presence of the six CF3 substituents on the terdentate phosphine. A similar effect may be responsible for the easier hydrolysis of the CF3PPP-containing, cationic rhodium(III) complexes relative to the corresponding compounds of the parent ligand. 相似文献
2.
Masahiro Ebihara Mitsuko Nomura Shogo Sakai Takashi Kawamura 《Inorganica chimica acta》2007,360(7):2345-2352
Reaction of tetrathiafulvalene carboxylic acid (TTFCO2H) with paddlewheel dirhodium complex Rh2(ButCO2)4 yielded TTFCO2-bridged complexes Rh2(ButCO2)3(TTFCO2) (1) and cis- and trans-Rh2(ButCO2)2(TTFCO2)2 (cis- and trans-2). Their triethylamine adducts [1(NEt3)2] and cis-[2(NEt3)2] were purified and isolated with chromatographic separation, and characterized with single crystal X-ray analysis. Trans-[2(NEt3)2] is not completely separated from a mixture of cis- and trans-[2(NEt3)2], but its single crystals were obtained from a solution of the mixture. A three-step quasi-reversible oxidation process was observed for 1 in MeCN. The first two steps correspond to the oxidation of the TTFCO2 moiety and the last one is the oxidation of the Rh2 core. The oxidation of cis-2 is observed as a two-step process with very similar E1/2 values to those of the first two processes for 1. Both 1+ and cis-22+ in MeCN at room temperature show isotropic ESR spectra with a g value of 2.008 and aH = 0.135 mT for two equivalent H atoms and aH = 0.068 mT for one H atom. The redox and ESR data of cis-2 suggest that the intramolecular interaction between the TTF moieties is very small. 相似文献
3.
A. M. Cano J. Cano T. Cuenca P. Gmez-Sal A. Manzanero P. Royo 《Inorganica chimica acta》1998,280(1-2):1
The reaction of TiCl4 with Li2[(SiMe2)2(η5-C5H3)2] in toluene at room temperature afforded a mixture of cis- and trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] in a molar ratio of 1/2 after recrystallization. The complex trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] was hydrolyzed immediately by the addition of water to THF solutions to give trans-[(TiCl2)2(μ-O){(SiMe2)2(η5-C5H3)2}] as a solid insoluble in all organic solvents, whereas hydrolysis of cis-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] under different conditions led to the dinuclear μ-oxo complex cis-[(TiCl2)2)(μ-O){(SiMe2)2(η5-C5H3)2}] and two oxo complexes of the same stoichiometry [(TiCl)2(μ-O){(SiMe2)2(η5-C5H3)2}]2(μ-O)2 as crystalline solids. Alkylation of cis- and trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] with MgCIMe led respectively to the partially alkylated cis-[(TiMe2Cl)2{(SiMe2)2(η5-C5H3)2}] and the totally alkylated trans-[(TiMe3)2{(SiMe2)2(η5-C5H3)2}] compounds. The crystal and molecular structure of the tetranuclear oxo complex [(TiCl)2(μ-O){(SiMe2)2(η5-C5H3)2}]2(μ-O)2 was determined by X-ray diffraction. 相似文献
4.
Irina V. Pisareva Igot T. Chizhevsky Pavel V. Petrovskii Eugenii V. Vorontzov Vladimir I. Bregadze Fedor M. Dolgushin Aleksandr I. Yanovsky 《Inorganica chimica acta》1998,280(1-2):233-237
The first η2-olefinic monocarbon metallacarbone closo-2-(Ph3P)-1-N,2-[μ-(η2-CH2CH=Ch2)]-1-N-(σ-CH2CH=CH2)-2,1- RhCB10H10 has been prepared by the reaction of the dimeric anion {[Ph3PRhB10H10CNH2]2-μ-H}−[PPN]+ with allyl bromide and characterized by a combination of spectroscopic methods and a single-crystal X-ray diffraction study. The variable temperature 1H and 13C NMR studies revealed the fluxional behavior of the η2-olefinic complex in CD2Cl2 solution which is associated with the allyl side-chain exchange process. 相似文献
5.
The preparation and structural characterization of {Ru3(CO)11}2(1,4-bis(diphenylphosphino)benzene), a modified synthesis of 1,4-bis(diphenylphosphino)benzene, and the structural characterization of {Ru3(CO)11}2(bis(diphenylphosphino)ethane) are reported. In both compounds two metal cluster units are connected through ditertiary-phosphine ligands. Both molecules consist of centrosymmetric units in which the diphosphine ligands are largely covered by the triangular ruthenium clusters. No direct interaction between the two cluster units occurs within individual molecules. Molecular packing in the solid state is dominated by interactions between sets of carbon monoxide ligands in motifs that were previously identified in the solid state structure of the parent cluster, Ru3(CO)12. 相似文献
6.
Oliver Renn Heinz Rüegger Luigi M. Venanzi Jürgen Gallus Volker Gramlich Arianna Martelletti 《Inorganica chimica acta》1995,240(1-2):575-580
It is shown that the reaction of RhCl3·3H2O with acetonitrile normally produces mixtures of mer- and fac-[RhCl3(CH3CN)3] (1a and 1b, respectively). The IR and 1H NMR spectra of these isomers were re-investigated. Their two-dimensional (103Rh,1H) NMR spectra were also recorded. Equilibrium and exchange studies of 1a and 1b in CD3C were performed. It was found that in 1a the exchange rate of the nitrile molecule trans to Cl is much faster than those of mutually trans nitriles. Also the nitrile molecules in 1b underwent fast exchange in CD3CN; however, their rate was slightly faster than that of the more labile CH3CN in 1a. The X-ray crystal structure of mer-[RhCl3(CH3CN)3]·CH3CN (1c) was determined. Crystal data: triclinic space group . 相似文献
7.
Elizabeth Babian-Kibala Hong Chen F. Albert Cotton Lee M. Daniels Larry R. Falvello Günter Schmid Zhengui Yao 《Inorganica chimica acta》1996,250(1-2):359-364
Compounds of formula [Al(CH3CN)6][MCl6]3(CH3CN)3 (M=Ta (1); Nb (2); Sb (3)) have been synthesized from the reactions of MCl5 and AlCl3 in acetonitrile and characterized by X-ray crystallography. Complex 1 crystallizes in the tetragonal space group P4/mbm with a = B = 10.408(2), C = 7.670(3) Å, V = 830.9(4) Å3 and Z = 2/3. Complex 2 crystallizes in the tetragonal space group P4/mnc with a = B = 330(a), C = 15.320(3) Å3 V = 1634.8(4) Å3 and Z = 4/3. Complex 3 also crystallizes in the tetragonal space group P4/mnc with a = B = 10.313(1), C = 15.238(2) Å, V = 1621.0(1) Å3 and Z = 4/3. The non-integer Z values for complexes 1–3 result unusual problems of disorder and/or twinning in these crystal structures due to their high symmetry. The M---Cl distances range from 2.329(3) Å in the Ta complex to 2.355(1) Å in the Sb complex, while the Al---N distances are similar in all three complexes, ranging from 1.92(1) to 1.97(1) Å, respectively. Complexes 1–3 are the first structurally characterized complexes that contain a (hexaacetonitrile)aluminum(III) cation. 相似文献
8.
Analogy with the isolable oxo cluster [Fe3(CO)9(μ3-O)]2−, which is structurally interesting and synthetically useful, prompted the present attempt to synthesize its ruthenium analog. Although the high reactivity of [Ru3(CO)9(μ3-O)]2− (I) prevented its isolation, the reaction of this species with [M(CO)3(NCCH3)]+, where M = Mn or Re, yields [PPN][MRu3(CO)12(η2-μ3-NC(μ-O)CH3]−. The high nucleophilicity of the oxo ligand in [Ru3(CO)9(μ3-O)]2− (I) appears to be responsible for the conversion of acetonitrile to an acetamidediato ligand and for the instability of I. The crystal structure of [PPN][MnRu3(CO)12(η2-μ3-NC(μ-O)CH3)]] reveals a hinged butterfly array of metal atoms in which the acetamidediato ligand bridges the two wings with μ3-N bonding to an Mn and two Ru atoms, and μ-O bonding to an Ru atom. 相似文献
9.
New mixed metal complexes SrCu2(O2CR)3(bdmap)3 (R = CF3 (1a), CH3 (1b)) and a new dinuclear bismuth complex Bi2(O2CCH3)4(bdmap)2(H2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi2O3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm−1. Crystal data for 1a: C27H51N6O9F9Cu2Sr/THF, monoclinic space group P21/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å3, Z = 2; for 1b: C27H60N6O9Cu2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å3, Z = 8; for 2: C22H48O11N4Bi2, monoclinic space group P21/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å3, Z = 4. 相似文献
10.
Ingo Brassat Ulli Englert Wilhelm Keim Dagmar P. Keitel Stefan Killat Gian-Paolo Suranna Ruimin Wang 《Inorganica chimica acta》1998,280(1-2):150-162
A series of cationic nickel complexes [(η3-methally)Ni(PP(O))]SbF6 (1–4) [PP(O) = Ph2P(CH2)P(O)Ph2 (dppmO) (1), Ph2P(CH2)2P(O)Ph2 (dppeO) (2), Ph2P(CH2)3P(O)Ph2 (dpppO) (3), pTol2P(CH2)P(O)pTol2 (dtolpmO) (4)] has been synthesized in good yields by treatment of [(η3-methally)NiBr]2 with biphosphine monoxides and AgSbF6. The ligands are coordinated in a bidentate way. Starting from [(η3-all)PdI]2 the cationic complexes [(η3-all)PP(O))]Y (8–14). [PP(O) = dppmO, dppeO, dpppO, dtolpmO;Y = BF4, SbF6, CF3SO3, pTolSO3] were synthesized in good yields. The coordination mode of the ligand is dependent on the backbone and the anion, revealing a monodentate coordination with dppmO for stronger coordinating anions. The intermediates [(η3-all)Pd(I)(PP(O)-κ1-P)] (5–7) [PP(O) = dppmO (5), dppeO (6), dtolpmO (7)] were isolated and characterized. Neutral methyl complexes [(Cl)(Me)Pd(PP(O))] (15–18). [PP(O) = dppmO (15), dppeO (16), dpppO (17), dtolpmO (18)] can easily be obtained in high yields starting from [(cod)PdCl2]. For dppmO two different routes are presented. The structure of [(Me)(Cl)Pd{;Ph2P(CH2-P(O)Ph2-κ2-P,O};] · CH2Cl2 (15) with the chlorine atom trans to phosphorus was determined by X-ray diffraction. 相似文献
11.
S. P. Gubin A. P. Klyagina I. F. Golovaneva T. V. Galuzina O. A. Belyakova Ya. V. Zubavichus Yu. L. Slovokhotov 《Inorganica chimica acta》1998,280(1-2):275-281
HRu2Fe2PdC(CO)12 (η3-ß-C10H15) cluster was prepared in the reaction of (Et4N) [HFe2Ru2C(CO)12] with [Pd(η3-ß-C10H15)Cl]2. X-ray structural study of HRu2Fe2PdC(CO)12 (η3-ß-C10H15) (where ß-C10H15 is ß-pinenyl) revealed a wing-tip butterfly geometry of the metal core and (1R, 2S, 3S, 5R) absolute configuration for both crystallography independent molecules in the crystal. Chiroptical properties of this cluster are compared with other clusters containing a Pd(η3-ß-C10H15) fragment and discussed. 相似文献
12.
The hydrothermal reactions of (Ph4P)[VO2Cl2] and H2C2O4 at 150 and 125°C yield (Ph4P)2[V2O2(H2O)2(C2O4)3]·4H2O (1) and (Ph4P)[VOCl(C2O4)] (2), respectively. The structure of the molecular anion of 1 consists of a binuclear unit of oxovanadium(IV) octahedra bridged by a bisbidentate oxalate group. The VO6 coordination geometry at each vanadium site is defined by a terminal oxo group, an aquo ligand, and four oxygen donors — two from the bisbidentate bridging oxalate and two from the terminal bidentate oxalate. The structure of 2 consists of discrete Ph4P+ cations occupying regions between [VOCl(C2O4)]−∞ spiral chains. The structure of the one-dimensional anionic chain exhibits V(IV) octahedra bridged by bisbidentate oxalate groups. Crystal data: 1·4H2O, monoclinic P21/n, A = 12.694(3), B = 12.531(3), C = 17.17(3) Å, β = 106.32(2)°, V = 2621.3(13) Å3, Z = 2, Dcalc = 1.501 g cm−3, structure solution and refinement converged at a conventional residual of 0.0518; 2, tetragonal P43, A = 12.145(2), C = 15.991(3) Å, V = 2358.7(12) Å3, Z = 4, R = 0.0452. 相似文献
13.
When a solution of [Co2(Ph2PCH2PPh2)(CO)6] in chloroform or deuterochloroform is allowed to stand in air at room temperature, it deposits dark green crystals of [Co{Ph2P(O)CH2P(O)Ph2}3][CoCl4] · 8CHCl3. The same product is formed more quickly and in much higher yield (80% based on Co) if the reaction is carried out in the presence of 2 equiv. of [Ph2PCH2PPh2]; the CoII appears to catalyse the air-oxidation of [Ph2PCH2PPh2]. The salt was characterised by X-ray crystallography and shown to contain octahedral CoII cations and CoII tetrahedral anions having normal bond lengths and angles. 相似文献
14.
V. Sreenivasa Reddy Kattesh V. Katti Charles L. Barnes 《Inorganica chimica acta》1995,240(1-2):367-370
The water-soluble bisphosphine, 1,2-bis(bis(hydroxymethyl)phosphino)ethane (1), was synthesized in near quantitative yield by the reaction of bisphosphine, H2PCH2CH2PH2, with an aqueous formaldehyde in the presence of K2PtCl4. The reaction of this water-soluble bisphosphine 1 with cis-Pt(COD)Cl2 affords the mononuclear bischelate complex, [Pt{(HOH2C)2PCH2CH2P(CH2OH)2}2](Cl)2 (2), in near quantitative yield. The new ligand and complex have been characterized spectroscopically and the structure of the metal complex, 2, was determined by X-ray crystallography. The Pt(II) complex 2 crystallizes in the orthorhombic space group Pbca(a=14.623(1), B=16.216(2), C=9.319(4) Å) with Z=4. The final R value is 0.024. 相似文献
15.
Michael A. Brook Bjrn Ramacher Carol Dallaire Hari K. Gupta Dagmar Ulbrich Ralph Ruffolo 《Inorganica chimica acta》1996,250(1-2):49-57
A series of tetrakis(trimethylsilylethyne) derivatives of Group 14 metals (2–4) was prepared. Co2(CO)6 complexes 5–10 were synthesised by the reaction of 2–4 with Co2(CO)8. From the silyl and germyl based compounds 2 and 3, either one or two alkynes could be complexed with Co2(CO)6. In contrast, the tin derived compound 4 could accommodate up to four Co2(CO)6 complexes. The longest wavelength UV-Vis absorbances of the silicon and germanium-based complexes were consistent with multiple, non-conjugated Co2(CO)6 chromophores. The tetrakis Co2(CO)6 complex 10, however, absorbs at a much longer wavelength suggesting conjugation of Co2(CO)6 complexes through the tin. The reactivity towards protonolysis of the uncomplexed alkynes 2–4 is a consequence of the hyperconjugative stabilisation of the intermediate β-vinyl cation (the β-effect): Sn(CCSiMe3)3>SnOTf(CCSiMe3)2>SiMe3>Ge(CCSiMe3)3. The reactivity of the Co2(CO)6 complexes, however, was quite different from the reactions of 2–4 and from analogous all-carbon systems. Treatment of 5–10 with strong acid led neither to protiodemetallation of the complexed or non-complexed alkynes but to decomplexation of the cobalt. Similarly, ligand metathesis reactions between 10 and Ph2SiCl2 were not observed. The normal reactivity of silylalkynes towards electrophiles, which was expected to be enhanced by the presence of the cobalt complex, was diminished by the particular steric environment of the molecules under examination (5–10). As a result, the favoured reaction under these conditions was decomplexation of the cobalt. 相似文献
16.
Oleg V. Gusev Mikhail A. Ievlev Konstantin A. Lyssenko Pavel V. Petrovskii Nikolai A. Ustynyuk Peter M. Maitlis 《Inorganica chimica acta》1998,280(1-2):249-256
The reaction of RuCl3(H2O), with C5Me4CF3J in refluxing EtOH gives [Ru2(η5-C5Me1CF2)2 (μ-Cl2] (20 in 44% yield. Dimer 2 antiferromagnetic (−2J=200 cm1). The crystal structures of 2 (rhombohedral system, R3 space group, Z=9, R=0.0589) and [Rh2(η5-C5Me4CF3(2Cl2(μ-Cl)2] (3) (rhombohedral system.
space group, Z = 9, R = 0.0641) were solved; both complexes have dimeric structures with a trans arrangement of the η5-C5Me4CF4 rings. Comparison of the geometry of 2 and 3 with those of the corresponding η5-C5Me5 complexes shows that lowering the ring symmetry causes significant distortion of the M2(μ-Cl)2 moiety. The analysis of the MCl3 fragment conformations in 2 and 3 and in the η5-C5ME5 analogues shows that they are correlated with the M---M distances. The Cl atoms are displaced by Br on reaction of 2 with KBr in MeOH to give the diamagnetic dimer [Ru2(η5-C5Me4CF3)2Br2 (μ-Br2] (4). Complex 2 reacts with O2 in CH2Cl2 solution at ambient temperature to form a mixture of isomeric η6-fulvene dimers [Ru2(η6-C5Me3CF3 = CH2)2Cl2(μ-Cl)2] (5). Reactions of 5 with CO and allyl chloride give Ru(η5-C5Me3CF3CH2Cl)(CO)2Cl (6) and Ru(η5-C5Me3CF3CF3CH2Cl)(η3-C3H5)Cl2 (7) respectively. 相似文献
17.
Masahiko Maekawa Megumu Munakata Takayoshi Kuroda-Sowa Yusaku Suenaga Kunihisa Sugimoto 《Inorganica chimica acta》1999,290(2):256-158
Two novel tetracopper(I) and tetrasilver(I) complexes [Cu4(atdz)6](ClO4)4·2CH3OH (1) and [Ag4(atdz)6](ClO4)4 (2), have been prepared using 2-amino-1,3,4-thiadiazole (atdz), and their crystal structures and properties have been determined. On each tetranuclear complex, two Cu or Ag atoms (M) are bridged by two atdz ligands to form a six-membered N2M2N2 framework. The two N2M2N2 frameworks are in parallel linked by another atdz ligand to provide the tetranuclear structure with a rectangular M4 core. The four Cu or Ag atoms possess a trigonal-square geometry. The two adjacent MM separations are (3.096(1) and 3.412(1) Å) and (3.316(2) and 3.658(2) Å) for 1 and 2, respectively. On both tetranuclear complexes there are two species of hydrogen bonds between the ClO4 − anions and the NH2 group of atdz ligands. It is proposed that the hydrogen bonds are related to the stabilization of the tetranuclear structure during the crystallization process. 相似文献
18.
Two ruthenium(II) complexes with polypyridyl, Ru(bipy)2(phen)](ClO4)2·H2O (1) and [Ru(bipy)2(Me-phen)](ClO4)2 (2), (phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine, Me-phen = 5-methyl-1,10-phenanthroline), were synthesized and characterized by IR, MS and NMR spectra. Their structures were determined by single crystal X-ray diffraction techniques. The strong steric interaction between the polypyridyl ligands was relieved neither by the elongation of the Ru---N bonds nor increase of the N---Ru---N bite angles. The coordination sphere was distorted to relieve the ligand interaction by forming specific angles (δ) between the polypyridyl ligand planes and coordination planes (N---Ru---N), and forming larger twisted angles between the two pyridine rings for each bipy. The bond distances of Ru---N(bipy) and Ru---N(phen) were virtually identical with experimental error, as expected of π back-bonding interactions which statistically involve each of the ligands present in the coordination sphere. 相似文献
19.
The reaction between the redox-active diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) and the dirhenium compound Re2(CO)8(μ-H)(μ-η1,η2-C CPh) in CH2Cl2 at room temperature proceeds by CO loss to give the dirhenium complex Re2(CO)7(bpcd)(μ-H)(η1-C CPh) (1). This new complex was characterized in solution by IR and NMR (1H and 31P) spectroscopy and in the solid state by X-ray diffraction analysis. Re2(CO)7(bpcd)(μ-H)(η1-C CPh) crystallizes in the triclinic space group
γ = 69.240(6)°, V = 2024.9(3) Å3, Z = 2, dcalc = 1.862 g cm−3 R = 0.0221, Rw = 0.243 for 4066 observed reflections. The bpcd ligand in 1 adopts a chelating mode with a linear phenylacetylide ligand being located on the adjacent rhenium center cis to the bpcd ligand. This complex represents the first structurally characterized example of a hydrido-bridged dirhenium complex possessing both a linear acetylide ligand and a chelating diphosphine ligand. 相似文献
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20.
Marcel Hoogenraad Kevita Ramkisoensing Willem L. Driessen Huub Kooijman Anthony L. Spek Elisabeth Bouwman Jaap G. Haasnoot Jan Reedijk 《Inorganica chimica acta》2001,320(1-2):117-126
New manganese(III) complexes of Hphox (2-(2′-hydroxyphenyl)-oxazoline) and HClphox (2-(5′-chloro-2′-hydroxyphenyl)-oxazoline) have been synthesised. The X-ray structures of [Mn(phox)2(MeOH)2][Mn(phox)2(ClO4)2](H2O)2 and [Mn(Clphox)2(MeOH)2](ClO4) show the manganese(III) ions to be octahedrally coordinated with methanol or perchlorate at the axial coordination sites. The cyclic voltammograms of the complexes, with the exception of [Mn(phox)2(acac)] (Hacac=2,4-pentanedione), show an irreversible reduction wave of manganese(III) to manganese(II). After addition of an excess of 1-methylimidazole (1-Meim), the reduction process shifts towards lower potentials and becomes (quasi-) reversible, indicating that the presence of 1-Meim affects the catalytic efficiency of the complexes. The complexes catalyse the epoxidation of styrene by dihydrogen peroxide. The cumulative turnover numbers towards styrene oxide obtained after 15 min. vary from 16 for [Mn(Clphox)2(MeOH)2](ClO4) to 26 for [Mn(phox)2(acac)]. Ligand degradation appears to be the limiting factor for obtaining higher turnover numbers. 相似文献