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1.
New mixed metal complexes SrCu 2(O 2CR) 3(bdmap) 3 (R = CF 3 (1a), CH 3 (1b)) and a new dinuclear bismuth complex Bi 2(O 2CCH 3) 4(bdmap) 2(H 2O) (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 SrF 2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi 2O 3 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), −2 J = 34.0(8) cm −1. Crystal data for 1a: C 27H 51N 6O 9F 9Cu 2Sr/THF, monoclinic space group P2 1/ m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å 3, Z = 2; for 1b: C 27H 60N 6O 9Cu 2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å 3, Z = 8; for 2: C 22H 48O 11N 4Bi 2, monoclinic space group P2 1/ c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å 3, Z = 4. 相似文献
2.
Reaction of RuCl(η 5-C 5H 5( pTol-DAB) with AgOTf (OTf = CF 3SO 3) in CH 2Cl 2 or THF and subsequent addition of L′ (L′ = ethene (a), dimethyl fumarate (b), fumaronitrile (c) or CO (d) led to the ionic complexes [Ru(η 5-C 5H 5)( pTol-DAB)(L′)][OTf] 2a, 2b and 2d and [Ru(η 5-C 5H 5)( pTol-DAB)(fumarontrile- N)][OTf] 5c. With the use of resonance Raman spectroscopy, the intense absorption bands of the complexes have been assigned to MLCT transitions to the iPr-DAB ligand. The X-ray structure determination of [Ru(η 5-C 5H 5)( pTol-DAB)(η 2-ethene)][CF 3SO 3] (2a) has been carried out. Crystal data for 2a: monoclinic, space group P2 1/ n with A = 10.840(1), b = 16.639(1), C = 14.463(2) Å, β = 109.6(1)°, V = 2465.6(5) Å 3, Z = 4. Complex 2a has a piano stool structure, with the Cp ring η 5-bonded, the pTol-DAB ligand σN, σN′ bonded (Ru-N distances 2.052(4) and 2.055(4) Å), and the ethene η 2-bonded to the ruthenium center (Ru-C distances 2.217(9) and 2.206(8) Å). The C = C bond of the ethene is almost coplanar with the plane of the Cp ring, and the angle between the plane of the Cp ring and the double of the ethene is 1.8(0.2)°. The reaction of [RuCl(η 5-C 5H 5)(PPh) 3 with AgOTf and ligands L′ = a and d led to [Ru(η 5-C 5H 5)(PPh 3) 2(L′)]OTf] (3a) and (3d), respectively. By variable temperature NMR spectroscopy the rottional barrier of ethene (a), dimethyl fumarate (b and fumaronitrile (c) in complexes [Ru(η 5-C 5H 5)(L 2)(η 2-alkene][OTf] with L 2 = iPr-DAB (a, 1b, 1c), pTol-DAB (2a, 2b) and L = PPh 3 (3a) was determined. For 1a, 1b and 2b the barrier is 41.5±0.5, 62±1 and 59±1 kJ mol −1, respectively. The intermediate exchange could not be reached for 1c, and the Δ G# was estimated to be at least 61 kJ mol −. For 2a and 3a the slow exchange could not be reached. The rotational barrier for 2a was estimated to be 40 kJ mol −. The rotational barier for methyl propiolate (HC≡CC(O)OCH 3) (k) in complex [Ru(η 5-C 5H 5)(iPr-DAB) η 2-HC≡CC(O)OCH 3)][OTf] (1 k) is 45.3±0.2 kJ mol −1. The collected data show that the barrier of rotational of the alkene in complexes 1a, 2a, 1b, 2b and 1c does not correlate with the strength of the metal-alkene interaction in the ground state. 相似文献
3.
Reactions of [(PPh 3) 2Pt(η 3-CH 2CCPh)]OTf with each of PMe 3, CO and Br − result in the addition of these species to the metal and a change in hapticity of the η 3-CH 2CCPh to η 1-CH 2CCPh or η 1-C(Ph)=C=CH 2. Thus, PMe 3 affords [(PMe 3) 3Pt(η 1-C(Ph)=C=CH 2)] +, CO gives both [ trans-(PPh 3) 2Pt(CO)(η 1-CH 2CCPh)] + and [ trans-(PPh 3) 2Pt(CO)(η 1-C(Ph)=C=CH 2)] +, and LiBr yields cis-(PPh 3) 2PtBr(η 1-CH 2CCPh), which undergoes isomerization to trans-(PPh 3) 2PtBr(η 1-CH 2CCPh). Substitution reactions of cis- and trans-(PPh 3) 2PtBr(η 1-CH 2CCPh) each lead to tautomerization of η 1-CH 2CCPh to η 1-C(Ph)=C=CH 2, with trans-(PPh 3) 2PtBr(η 1-CH 2CCPh) affording [(PMe 3) 3Pt(η 1-C(Ph)=C=CH 2)] + at ambient temperature and the slower reacting cis isomer giving [ trans-(PPh 3)(PMe 3) 2Pt(η 1-C(Ph)=C=CH 2)] + at 54 °C . All new complexes were characterized by a combination of elemental analysis, FAB mas spectrometry and IR and NMR ( 1H, 13C{ 1H} and 31P{ 1H}) spectroscopy. The structure of [(PMe 3) 3Pt(η 1-C(Ph)=C=CH 2)]BPh 4·0.5MeOH was determined by single-crystal X-ray diffraction analysis. 相似文献
4.
The reactions of complex (C 5Me 5)Ir(Cl) (CO) (Me) (1a) with cyclohexylisocyanide and phosphines (L=CyNC, PHPh 2, PMePh 2, PMe 2Ph) give the products of alkyl migratory insertion (C 5Me 5Ir(Cl) (COMe) (L), in toluence or tetrahydrofuran at 323 K or higher temperature. The phenyl analogue (C 5Me 5)Ir(Cl)(CO)(Ph) or the iodide complexes (C 5Me 5)Ir(I) (CO) (R) (R=Me, Ph_are not reactive under the same conditions. The reaction of (C 5Me 5)Ir(Cl)(CO)(Me) with PMePh 2 and PMe 2Ph in acetonitrile yields the chloride substitution product [(C 5Me 5)Ir(CO)(L)(Me)] +Cl −. Kinetic measurements for the reactions of (C 5Me 5)Ir(Cl)(CO)(Me) in toluene are first order in the iridium complex and exhibit a saturation dependence on the incoming donors L. Analysis of the data suggests a two-step process involving (i) rapid formation of a molecular complex [(C 5Me 5)Ir(Cl)(CO)(Me), (L)], in which the structure of 1a is unperturbed within the limits of spectroscopic analysis, and (ii) rate determining methyl migration. The reaction parameters are K for the pre-equilibrium step ( K = 1.5 (CyNC), 7.3 (PHPh 2), 7.1 (PMePh 2) dm 3 mol −1 at 323 K) and k2 for the slow carbon---carbon bond formation ( k2 (10 5) = 6.9 (CyNC), 1.2 (PHPh 2), 1.0 (PMePh 2) s −1 at 323 K). The activation parameters for the methyl migration step in the reaction with PMePh 2 obtained between 308 and 338 K, are Δ H≠ = 106±16 kJ mol −1 and Δ S≠ = − 14±5 J K −1 mol −1. The reaction of 1a with PMePh 2 proceeds at similar rates in tetrahydrofuran ( K = 3.7 dm 3 mol −1, k2 (10 5) = 1.2 s −1, 323 K). The crystal structure of (C 5Me 5)Ir(Cl)(COMe) (PMe 2Ph) has been determined by X-ray diffraction. C 20H 29ClOPIr: Mr = 544.1, monoclinic, P2 1/ n, A = 8.084 (2), B = 9.030(2), C = 28.715 (3) Å, β = 91.41 (3)°, Z = 4, Dc = 1.71 g cm −3, V = 2095.5 Å 3, room temperatyre, Mo K, γ = 0.71069, μ = 65.55 cm −1, F(000) = 1044, R = 0.037 for 2453 independent observed reflections. The complex shows a deformed tetrahedral coordination assuming the η 5-C 5Me 5 molecular fragment as a single coordination site. The iridium-chlorine bond is staggered with respect to two adjacent C(ring)-methyl bonds, while the Ir---P and the Ir---COMe bonds are eclipsed with respect to C(ring)-methyl bonds. 相似文献
5.
The dialkyl-μ-ethylidene-μ-methylene-bis (pentamethylcyclopentadienyl)-dirhodium complexes [{(C 5Me 5)Rh} 2(μ-CH 2)(μ-CHMe) (R) 2] (4, P=Me; 5, Et; 6, n-Bu; 7, CH=CH 2; and 8, Z-CH=CHMe) have been prepared from RMgBr and [{(C 5Me 5)Rh} 2(μ-CH 2)(μ-CHMe)(X) 2] (2, X=Cl; 3, X=Br). Structures deduced from the NMR spectra show that the dialkyl complexes can exist in one trans and two cis forms. The decomposition of the dimethyl complex 4 is compared with that of the related di-μ-methylene complex; it reacts readily (30°C, MeCN solution) in the presence of one-electron oxidisers to give propene and methane and a little ethene and some butenes. Mass-spectrometric analysis of the 13C labelling in the organics originating from [{(C 5Me 5)Rh} 2(μ-CH 2)(μ-CHMe) ( 13CH 3) 2] shows that methane derives from the Rh---Me, ethene half from the ethylidene and half from coupling of Rh-methyl and a bridging methylene, while the propene arises almost entirely from the ethylidene and a rhodium methyl. The butenes come from coupling of ethylidene, methylene and a Rh-methyl, but only quite small amounts are formed; thus C+C coupling is the major decomposition path for the μ-ethylidenes, in contrast to the di-μ-methylene complexes where C+C+C coupling predominates. The divinyl complex [{(C 5Me 5)Rh} 2(μ-CH 2)(μ-CHMe) (CH=CH 2) 2] also underwent internal C+C coupling on reaction with AgBF 4 in MeCN to give a mixture of the allyl and methylallyl cations [(C 5Me 5)Rh(η 3-CH 2CHCHR)(MeCN)] +(10, R=H; 11, R=Me). 相似文献
6.
The reaction of thiamine with K 2Pt IICl 4 and with Pt IVCl 4 in the presence of excess NaSCN in aqueous solution gave thiamine salts, (H-thiamine)[Pt(SCN) 4] · 3H 2O (1) and (H-thiamine)[Pt(SCN) 6] · H 2O (2), respectively, structures of which have been determined by X-ray diffraction. The thiamine molecule adopts the usual F conformation in each salt. In 1, [Pt(SCN) 4] 2− ions act as large planar spacers in the crystal lattice and interact scarcely with thiamine, except for a hydrogen bonding with the terminal hydroxy O(5 γ). Instead, water molecules form two types of host–guest-like interactions with the pyrimidine and the thiazolium moieties of a thiamine molecule, one being a C(2)–Hwaterpyrimidine bridge and the other being an N(4′)–Hwaterthiazolium bridge. In 2, despite the much larger ion size, octahedral [Pt(SCN) 6] 2− ions form a C(2)–Hanionpyrimidine bridge and an N(4′)–Hanionthiazolium bridge. An additional hydrogen bonding between the anion and the terminal O(5γ) of thiamine creates a hydrogen-bonded macrocyclic ring {thiaminium–[Pt(SCN) 6] 2−} 2, a supramolecule. 相似文献
7.
The reversible equilibrium conversion under H 2 of [RuCl(dppb) (μ-Cl)] 2 (1) to generate (η 2-H 2) (dppb) (μ-Cl) 3RuCl(dppb) in CH 2Cl 2 (dppb = Ph2P( CH2) 4PPh2) has been studied at 0–25 °C by UV-Vis and 31P{ 1H} NMR spectroscopy, and by stoppe kinetics; the equilibrium constant and corresponding thermodynamic parameters, and the forward and reverse rate constants at 25 °C have been determined. A measured Δ H° value of 0 kJ mol −1 allows for an estimation of an exothermicity of 60 kJ mol −1 for binding an η 2-H 2 at an Ru(II) centre; a Δ S° value of 60 J mol −1 K −1 indicates that in solution 1 contain s coordinated CH 2Cl 2. The kinetic and thermodynamic data are compared to those obtained from a previously studied hydrogenation of styrene catalyzed by 1. Preliminary findings on related systems containing Ph 2P(CH 2) 3PPh 2 and (C 6H 11) 2P(C 6H 11) 2 are also noted. 相似文献
8.
The phosphinoalkenes Ph 2P(CH 2) nCH=CH 2 ( n= 1, 2, 3) and phosphinoalkynes Ph 2P(CH 2) n C≡CR (R = H, N = 2, 3; R = CH 3, N = 1) have been prepared and reacted with the dirhodium complex (η−C 5H 5) 2Rh 2(μ−CO) (μ−η 2−CF 3C 2CF 3). Six new complexes of the type (ν−C 5H 5) 2(Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3)L, where L is a P-coordinated phosphinoalkene, or phosphinoalkyne have been isolated and fully characterized; the carbonyl and phosphine ligands are predominantly trans on the Rh---Rh bond, but there is spectroscopic evidence that a small amount of the cis-isomer is formed also. Treatment of the dirhodium-phosphinoalkene complexes with (η−CH 3C 5H 4)Mn(CO) 2thf resulted in coordination of the manganese to the alkene function. The Rh 2---Mn complex [(η−C 5H 5) 2Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3) {Ph 2P(CH 2) 3CH=CH 2} (η−CH 3C 5H 4)Mn(CO) 2] was fully characterized. Simi treatment of the dirhodium-phosphinoalkyne complexes with Co 2(CO) 8 resulted in the coordination of Co 2(CO) 6 to the alkyne function. The Rh 2---Co 2 complex [(η−C 5H 5) 2Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3) {Ph 2PCH 2C≡CCH 3}Co 2(CO) 2], C 37H 25Co 2F 6O 7PRh 2, was fully characteriz spectroscopically, and the molecular structure of this complex was determined by a single crystal X-ray diffraction study. It is triclinic, space group
( Ci1, No. 2) with a = 18.454(6), B = 11.418(3), C = 10.124(3) Å, = 112.16(2), β = 102.34(3), γ = 91.62(3)°, Z = 2. Conventional R on | F| was 0.052 fo observed ( I > 3σ( I)) reflections. The Rh 2 and Co 2 parts of the molecule are distinct, the carbonyl and phosphine are mutually trans on the Rh---Rh bond, and the orientations of the alkynes are parallel for Rh 2 and perpendicular for Co 2. Attempts to induce Rh 2Co 2 cluster formation were unsuccessful. 相似文献
9.
The ligand N, N′-bis[2,2-dimethyl-4-(2-hydroxyphenyl)-3-aza-3-buten] oxamide with two identical coordination sites reacts with copper ions in its tetradeprotonated form to yield the dinuclear complex [Cu 2(C 24H 26N 4O 4)]·H 2O. The structure of this compound has been determined by the X-ray diffraction method. The crystals are orthorhombic with a = 11.744(1), B = 16.369(2), C = 26.340(3) Å, V = 5064(1) Å 3, Z = 8, space group Pbca. The oxamide is in a trans conformation with two different environments for the copper centres, a (4 + 1) coordination mode for the first one and a square planar environment for the other one. The water molecule is not directly bound to a copper centre, but involved in hydrogen bonding with the two oxygen atoms of an N 2O 2 coordination site. Indeed, extra coordination comes from a phenolic oxygen atom belonging to an adjacent dinuclear unit. Static susceptibility measurements point to a strong intrapair antiferromagnetic exchange interaction of 2 J = −520(±4) cm −1 and possibly an interpair ferromagnetic exchange interaction of 10(±5) cm −1. 相似文献
10.
The hydrothermal reactions of (Ph 4P)[VO 2Cl 2] and H 2C 2O 4 at 150 and 125°C yield (Ph 4P) 2[V 2O 2(H 2O) 2(C 2O 4) 3]·4H 2O (1) and (Ph 4P)[VOCl(C 2O 4)] (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 VO 6 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 Ph 4P + cations occupying regions between [VOCl(C 2O 4)] −∞ spiral chains. The structure of the one-dimensional anionic chain exhibits V(IV) octahedra bridged by bisbidentate oxalate groups. Crystal data: 1·4H 2O, monoclinic P2 1/ n, A = 12.694(3), B = 12.531(3), C = 17.17(3) Å, β = 106.32(2)°, V = 2621.3(13) Å 3, Z = 2, Dcalc = 1.501 g cm −3, structure solution and refinement converged at a conventional residual of 0.0518; 2, tetragonal P4 3, A = 12.145(2), C = 15.991(3) Å, V = 2358.7(12) Å 3, Z = 4, R = 0.0452. 相似文献
11.
Two novel, weakly antiferromagnetically coupled, tetranuclear copper(II) complexes [Cu 4(PAP) 2(μ 2-1,1-N 3) 2(μ 2-1,3-N 3) 2(μ 2-CH 3OH) 2(N 3) 4 (1) (PAP = 1,4-bis-(2′-pyridylamino)phthalazine) and [Cu 4(PAP3Me) 2 (μ 2-1,1-N 3) 2(μ 2-1,3-N 3) 2(H 2O) 2(NO 2) 2]- (NO 3) 2 (2) (PAP3Me = 1,4-bis-(3′-methyl-2′-pyridyl)aminophthalazine) contain a unique structural with two μ 2-1,1-azide intramolecular bridges, and two μ 2-1,3-azide intermolecular bridges linking pairs of copper(II) centers. Four terminal azide groups complete the five-coordinate structures in 1, while two terminal waters and two nitrates complete the coordination spheres in 2. The dinuclear complexes [Cu 2(PPD)(μ 2-1,1-N 3)(N 3) 2(CF 3SO 3)]CH 3OH) (3) and [Cu 2(PPD)(μ 2-1,1-N 3)(N 3) 2(H 2O)(ClO 4)] (4) (PPD = 3,6-bis-(1′-pyrazolyl)pyridazine) contain pairs of copper centers with intramolecular μ 2-1,1-azid and pyridazine bridges, and exhibit strong antiferromagnetic coupling. A one-dimensional chain structure in 3 occurs through intermolecular μ 2-1,1-azide bridging interactions. Intramolecular Cu-N 3-Cu bridge angles in 1 and 2 are small (107.9 and 109.4°, respectively), but very large in 3 and 4 (122.5 and 123.2°, respectively), in keeping with the magnetic properties. 2 crystallizes in the monoclinic system, space group C2/ c with a = 26.71(1), b = 13.51(3), c = 16.84(1) Å, β = 117.35(3)° and R = 0.070, Rw = 0.050. 3 crystallizes in the monoclinic system, space group P2 1/ c with a = 8.42(1), b = 20.808(9), c = 12.615(4) Å, β = 102.95(5)° and R = 0.045, Rw = 0.039. 4crystallizes in the triclinic system, space group P1, with a = 10.253(3), b = 12.338(5), c = 8.072(4) Å, = 100.65(4), β = 101.93(3), γ = 87.82(3)° and R = 0.038, Rw = 0.036 . The magnetic properties of 1 and 2 indicate the presence of weak net antiferromagnetic exchange, as indicated by the presence of a low temperature maximum in χ m (80 K (1), 65 K (2)), but the data do not fit the Bleaney-Bowers equation unless the exchange integral is treated as a temperature dependent term. A similar situation has been observed for other related compounds, and various approaches to the problem will be discussed. Magnetically 3 and 4 are well described by the Bleaney-Bowers equation, exhibiting very strong antiferromagnetic exchange (− 2 J = 768(24) cm −1 (3); − 2 J = 829(11) cm −1 (4)). 相似文献
12.
An improved synthetic procedure for pentabenzylcyclopentadiene Bz 5C 5H was developed. Six new organomolybdenum and organotungsten halides η 5-Bz 5C 5M(CO) 3X(M = Mo, W; X = Cl, Br, I) were syntesized through the reaction of η 5-Bz 5C 5M(CO) 3Li (derived from Bz 5C 5H, n-BuLi and M(CO) 6) with PCl 3, PBr 3 or I 2 and characterized by elemental analysis, IR and 1H NMR spectroscopy. The structure of η 5-Bz 5C 5Mo(CO) 3I was determined by single-crystal X-ray diffraction techniques. It crystallized in the monoclinic space groupp P2/ c with cell parameters a = 13.294(4), B = 15.147(4), C = 19.027(3) Å, β = 108.32(2)°, V = 3637(2) Å 3, Z = 4 and Dx = 1.50 g cm −3. The final R value was 0.035 for 4564 observed reflections. 相似文献
13.
1. Single reduced methyl viologen (MV .+) acts as an electron donor in a number of enzyme systems. The large changes in extinction coefficient upon oxidation (λ max 600 nm; MV .+, = 1.3 · 10 4 M −1 · cm −1; oxidised form of methyl viologen (MV 2+), = 0.0) make it ideally suited to kinetic studies of electron transfer reactions using stopped-flow and standard spectrophotometric techniques. 2. A convenient electrochemical preparation of large amounts of MV.+ has been developed. 3. A commercial stopped-flow apparatus was modified in order to obtain a high degree of anaerobicity. 4. The reaction of MV.+ with O2 produced H2O2 (k > 5 · 106 M−1 · s−1, pH 7.5, 25 °C). H2O2 subsequently reacted with excess MV.+ (k = 2.3 · 103 M−1 · s−1, pH 7.5, 25 °C) to produce water. The kinetics of this reaction were complex and have only been interpreted over a limited range of concentrations. 5. The results support the theory that the herbicidal action of methyl viologen (Paraquat, Gramoxone) is due to H2O2 (or radicals derived from H2O2) induced damage of plant cell membrane. 相似文献
14.
The syntheses and structures of [Ni(H 2O) 6] 2+[MF 6] 2− (M = Ti,Zr,Hf) and Ni 3(py) 12F 6·7H 2O are reported. The former three compounds are isostructural, crystallizing in the trigonal space group
(No. 148) with Z = 3. The lattice parameters are a = 9.489(4), C = 9.764(7) Å, with V = 761(1) Å 3 for Ti; a = 9.727(2), C = 10.051(3) Å, with V = 823.6(6) Å 3 for Zr; and a = 9.724(3), C = 10.028(4)Å, with V = 821.2(8)Å 3 for Hf. The structures consist of discrete [Ni(H 2O) 6] 2+ and [MF 6] 2− octahedra joined by O---HF hydrogen bond Large single crystals were grown in an aqueous hydrofluoric acid solution. Ni 3(py) 12F 6·7H 2O crystallizes in the monoclinic space group I2/ a (No. 15) with Z = 4. The lattice parameters are a = 16.117(4), B = 8.529(3), C = 46.220(7) Å, β = 92.46(2)°, and V = 6348(5) Å 3. The structure consists of discrete Ni(py) 4F 2 octahedra linked through H---O---HF and H---O---HO hydrogen bonding interactions. Single c were grown from a (HF) x·pyridine/pyridine/water solution. 相似文献
15.
Treatment of the A-ring aromatic steroids estrone 3-methyl ether and β-estradiol 3, 17-dimethyl ether with Mn(CO) 5+BF 4− in CH 2Cl 2 yields the corresponding [(steroid)Mn(CO) 3]BF 4 salts 1 and 2 as mixtures of and β isomers. The X-ray structure of [(estrone 3-methyl ether)Mn(CO) 3]BF 4 · CH 2Cl 2 (1) having the Mn(CO) 3 moiety on the side of the steroid is reported: space group P2 1 with a=10.3958(9), b=10.9020(6), c=12.6848(9) Å, β=111.857(6)°, Z=2, V=1334.3(2) Å 3, calc=.481 cm −3, R=0.0508, and wR=0.0635. The molecule has the traditional ‘piano stool’ structure with a planar arene ring and linear Mn---C---O linkages. The nucleophiles NaBH 4 and LiCH 2C(O)CMe 3 add to [(β-estradiol 3,17-dimethyl ether)Mn(CO) 3]BF 4 (2) in high yield to give the corresponding - and β-cyclohexadienyl manganese tricarbonyl complexes (3). The nucleophiles add meta to the arene -OMe substituent and exo to the metal. The and β isomers of 3 were separated by fractional crystallization and the X-ray structure of the β isomer with an exo-CH 2C(O)CMe 3 substituent is reported (complex 4): space group P2 12 12 1 with a=7.5154(8), b=15.160(2), c=25.230(3) Å, Z=4, V=2874.4(5) Å 3, calc=1.244 g cm −3, R=0.0529 and wR2=0.1176. The molecule 4 has a planar set of dienyl carbon atoms with the saturated C(1) carbon being 0.592 Å out of the plane away from the metal. The results suggest that the manganese-mediated functionalization of aromatic steroids is a viable synthetic procedure with a range of nucleophiles of varying strengths. 相似文献
16.
Complexes of type A 4[VO(tart)] 2· nH 2O, where A = Rb or Cs and tart = d, l-tartrate(4−) ( n = 2) or d,d-tartrate(4−) ( n = 2 for Rb and n = 3 for Cs), were prepared from an aqueous mixture of V 2O 5, AOH and H 4tart. These complexes were studied by single-crystal X-ray diffraction methods: Rb 4[VO( d, l-tart)] 2·2H 2O, space group P1 with a = 8.156(1), b = 8.246(1), c = 8.719(1)Å, = 66.09(1)°, β = 65.07(1)°, γ = 82.40(1)°, Z = 2, 1917 observed reflections, and final Rw = 0.035; Cs 4[VO( d, l-tart)] 2·2H 2O, space group P21/ c with a = 9.350(1), b = 13.728(2), c = 8.479(1)Å, β = 106.77(1)°, Z = 4, 2235 observed reflections, and final Rw = 0.054; Rb 4[VO( d, d-tart)] 2·2H 2O, space group P4122 with a = 8.072(1), c = 32.006(3)Å, Z = 8, 1014 observed reflections and final Rw = 0.038; Cs 4[VO( d, d-tart)] 2·3H 2O, space group P122 with a = 8.184(1), c = 33.680(5)Å, Z = 8, 1310 observed reflections, and final Rw = 0.063. Bulk magnetic susceptibility data (1.5–300 K) for these compounds and A 4[VO l, l-tart)] 2· nH 2O (A = Rb, Cs) were obtained on polycrystalline samples. These data were analyzed in terms of a Van Vleck exchange coupled S = 1/2 model which was modified to include an interdimer exchange parameters Θ. Analysis of the low-temperature (1.5–20 K) susceptibility data gave 2 J = +1.30 cm −1 and Θ = −1.86 K for Rb 4[VO( d, l-tart)] 2·2H 2O, 2 J = +1.16 cm −1 and Θ = −1.69 K for Cs 4[VO( d, l-tart)] 2·2H 2O, 2 J = +1.90 cm −1 and Θ = −0.82 K for Rb 4[VO( d, d-tart)] 2·2H 2O, 2 J = +2.04 cm −1 and Θ = −0.80 K for Rb 4[VO( l, l-tart)] 2·2H 2O, 2 J = +1.52 cm −1 and Θ = −0.25 K for Cs 4[VO( d, d-tart)] 2·3H 2O, and 2 J = +1.64 cm −1 and Θ = −0.31 K for Cs 4[VO( l, l-tart)] 2·3H 2O. These results suggest the magnitudes of intradimer (ferromagnetic and interdimer (antiferromagnetic) exchange interactions are similar in these complexes, as observed for the analogous Na salts. 相似文献
17.
Reaction of (NEt 4) 2MS 4 (M = Mo, W) with CuCl and KSCN (or NH 4SCN) in acetone or acetonitrile affords a new set of mixed metal–sulfur compounds: infinite anionic chains Cu 4(NCS) 5MS 43− (1,2), (CuNCS) 3WS 42− (3) and two dimensional polymeric dianions (CuNCS) 4MS 42− (4,5). Crystal of 1 (M = W) and 3 are triclinic, space group P1(1: a = 10.356(2), b = 15.039(1), c = 17.356(2)Å, = 78.27(1)°, β = 88.89(2)° and γ = 88.60(1)°, Z = 2, R = 0.04 for 3915 independent data;3: a = 8.449(2), b = 14.622(4), c = 15.809(8)Å, = 61.84(3)°, β = 73.67(3)° and γ = 78.23(2)°, Z = 2, R = 0.029 for 6585 independent data). Crystals of 4 (M = W) and 5 (M = Mo) are monoclinic, space group P2 1/ m, Z = 2 (4: a = 12.296(4), b = 14.794(4), c = 10.260(3)Åand β = 101.88(3)°, R = 0.034 for 4450 independent data;5: a = 12.306(2), b = 14.809(3), c = 10.257(2)Åand β = 101.99(3)°, R = 0.043 for 3078 independent data). The crystal structure determinations of 4 and 5 show that four edges of the tetrahedral MS 42− core are coordinated by copper atoms forming WS 4Cu 4 aggregates linked by eight-membered Cu(NCS) 2Cu rings. A two-dimensional network is thus formed in the diagonal (101) plane. The space between the anionic two-dimensional networks is filled with the NEt 4+ cations. Additional NCS groups lead to the [Cu 4(NCS) 5WS 4] 3− (1) trianion connected by NCS bridges forming pseudo-dimers. These latter are held together by weak CuS(NCS) interactions giving rise to infinite chains along a direction parallel to [100]. In contrast complex3 develops infinite chains from WS 4Cu 3 aggregates with the same Cu(NCS) 2Cu bridges as in 4 and 5. These chains are running along a direction parallel to [010]. The structural data of the different types of polymeric compounds containing MS 42− and CuNCS have been used to interpret vibrational spectroscopic data of the thiocyanate groups. 相似文献
18.
Three new crystalline tin selenide salts have been prepared from the reactions of [PPh 4] 2[Sn(Se 43] in supercritical solvents. The starting material pyrolyzes in supercritical acetonitrile to form [PPh 4] 4[Sn 6Se 21] (I), and it also reacts with SnSe in supercritical ammonia leading to a mixture of [PPh 4] 4[Sn 3Se 11] 2 (II). and [PPh 4] 2[Sn(Se 4)(Se 6) 2] (III). All three compounds have been characterized by single crystal X-ray diffraction. Crystallographic data: for I, C 96H 90P 4Se 21Sn 6, space group triclinic, P-1, A = 18.763(3), B = 24.600(4), C = 13.137(1) Å, = 102.63(1), β = 93.66(1), γ = 108.72(1)°, V = 5544(1) Å 3, Z = 2, R = 0.0350, RW = 0.0317: for II, C 96H 80P 4Se 22Sn 6, space group monoclinic P2 1/ c, A = 31.500(4), B = 16.572(3), C = 22.352(3) Å, β = 103.53(1)°, V = 11344(3) Å 3, Z = 4, R = 0.0771, RW = 0.0664: for III, C 48H 40P 2Se 16Sn, space group monoclinic, C2/ c, A = 25.381(2), B = 13.934(4), C = 19.465(3) Å, β = 121.587(8)°, V = 5867(2) Å 3, Z = 4, R = 0.0807, RW = 0.0650. One of the compounds, [PPh 4] 2[Sn(Se 4(Se 62], is a molecular cluster while the other two complexes [PPh 4] 4[Sn 3Se 11] 2 and [PPh 4] 4[Sn 6Se 21], are one dimensional tin selenide chains. The structures of the two chains are related and consits of tetrahedral and distorted trigonal bipyramidal tin(IV) centers bridged by Se 2−, Se 22− and Se 32− chains. 相似文献
19.
The stability constants of the 1:1 complexes formed between Cu(Arm) 2+, where Arm = 2,2′-bipyridyl or 1,10-phenanthroline, and methyl phosphate, CH 3OPO 32−, or hydrogen phosphate, HOPO 32−, were determined by potentiometric pH titration in aqueous solution (25°C; l = 0.1 M, NaNO 3). On the basis of previously established log K versus p Ka straight-line plots (D. Chen et al., J. Chem. Soc., Dalton Trans. (1993) 1537–1546) for the complexes of simple phosphate monoesters and phosphonate derivatives, R-PO 32−, where R is a non-coordinating residue, it is shown that the stabilities of the Cu(Arm) (CH 3OPO 3) complexes are solely determined by the basicity of the -PO 32− residue. In contrast, the Cu(Arm) (HOPO 3) complexes are slightly more stable (on average by 0.15 log unit) than expected on the basicity of HPO 42−; this is possibly due to a more effective solvation including hydrogen bonding, an interaction not possible with coordinated CH 3OPO 32− species. Regarding biological systems the observation that HOPO 32− is somewhat favored over R-PO 32− species in metal ion interactions is meaningful. 相似文献
20.
Rapid reactions occur between [Os VI(tpy)(Cl) 2(N)]X (X = PF 6−, Cl −, tpy = 2,2′:6′,2″-terpyridine) and aryl or alkyl phosphi nes (PPh 3, PPh 2Me, PPhMe 2, PMe 3 and PEt 3) in CH 2Cl 2 or CH 3CN to give [Os IV(tpy)(Cl) 2(NPPh 3)] + and its analogs. The reaction between trans-[Os VI(tpy)(Cl) 2(N)] + and PPh 3 in CH 3CN occurs with a 1:1 stoichiometry and a rate law first order in both PPh 3 and Os VI with k(CH 3CN, 25°C) = 1.36 ± 0.08 × 10 4 M − s −1. The products are best formulated as paramagnetic d 4 phosphoraniminato complexes of Os IV based on a room temperature magnetic moment of 1.8 μ B for trans-[Os IV(tpy)(Cl) 2(NPPh 3)](PF 6), contact shifted 1H NMR spectra and UV-Vis and near-IR spectra. In the crystal structures of trans-[Os IV(tpy)(Cl) 2( NPPh 3)](PF 6)·CH 3CN (monoclinic, P2 1/ n with a = 13.384(5) Å, b = 15.222(7) Å, c = 17.717(6) Å, β = 103.10(3)°, V = 3516(2) Å 3, Z = 4, Rw = 3.40, Rw = 3.50) and cis-[Os IV(tpy)(Cl) 2(NPPh 2Me)]-(PF 6)·CH 3CN (monoclinic, P2 1/ c, with a = 10.6348(2) Å, b = 15.146(9) ÅA, c = 20.876(6) Å, β = 97.47(1)°, V = 3334(2) Å 3, Z = 4, R = 4.00, Rw = 4.90), the long Os-N(P) bond lengths (2.093(5) and 2.061(6) Å), acute Os-N-P angles (132.4(3) and 132.2(4)°), and absence of a significant structural trans effect rule out significant Os-N multiple bonding. From cyclic voltammetric measurements, chemically reversible Os V/IV and Os IV/III couples occur for trans-[Os IV(tpy)(Cl) 2(NPPh 3)](PF 6) in CH 3CN at +0.92 V (Os V/IV) and −0.27 V (Os IV/III) versus SSCE. Chemical or electrochemical reduction of trans-[Os IV(tpy)(Cl) 2(NPPh 3)](PF 6) gives isolable trans-Os III(tpy)(Cl) 2(NPPh 3). One-electron oxidation to Os V followed by intermolecular disproportionation and PPh 3 group transfer gives [Os VI(tpy)Cl 2(N)] +, [OS III(tpy)(Cl) 2(CH 3CN)] + and [Ph 3=N=PPh 3] + (PPN +). trans-[Os IV(tpy)(Cl) 2(NPPh 3)](PF 6) undergoes reaction with a second phosphine under reflux to give PPN + derivatives and Os II(tpy)(Cl) 2(CH 3CN) in CH 3CN or Os II(tpy)(Cl) 2(PR 3) in CH 2Cl 2. This demonstrates that the Os VI nitrido complex can undergo a net four-electron change by a combination of atom and group transfers. 相似文献
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