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1.
Ferreira GB Hollauer E Comerlato NM Wardell JL 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):681-689
As shown previously by X-ray structure determinations, [tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate(IV)](2-) salts, [Q](2)[Sn(dmit)(3)], contain isolated cations and dianions. While the tin centres generally having octahedral geometries, the overall shapes of the dianions of these complexes in the solid state can differ with conformations varying from T, Y to asymmetrical arrangements. We now report, as a follow up to our earlier study on the Y-shaped complex, [NEt(4)](2)[Sn(dmit)(3)], an experimental and theoretical study of the vibrational spectra of solid solvated {[AsPh(4)](2)[Sn(dmit)(3)] x Me(2)CO}, in which the dianion has a T-shaped conformation. The infrared and Raman spectra, recorded from 4000 to 150 cm(-1), have been analysed by different ab initio calculations based on restricted Hartree-Fock (RHF) and density functional theory (DFT-Beck3LYP). The calculations were carried out on isolated dianions and cations with the 6-31G and 6-31G(d) basis sets and effective core potentials of Steven, Bash and Krauss (SBK). Fundamentals, overtones and combinations have been assigned. Generally, the Y- and T-shaped dianions exhibit similar infrared/Raman spectra, apart from differences in the C=C and the symmetrical M-S stretching frequencies: such differences can be used diagnostically to distinguish the overall shape of the tris(chelated)metallate dianion. 相似文献
2.
Sellmann D Geipel F Heinemann FW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):958-966
In the search for complexes modeling the [Fe(CN)(2)(CO)(cysteinate)(2)] cores of the active centers of [NiFe] hydrogenases, the complex (NEt(4))(2)[Fe(CN)(2)(CO)('S(3)')] (4) was found ('S(3)'(2-)=bis(2-mercaptophenyl)sulfide(2-)). Starting complex for the synthesis of 4 was [Fe(CO)(2)('S(3)')](2) (1). Complex 1 formed from [Fe(CO)(3)(PhCH=CHCOMe)] and neutral 'S(3)'-H(2). Reactions of 1 with PCy(3) or DPPE (1,2-bis(diphenylphosphino)ethane) yielded diastereoselectively [Fe(CO)(2)(PCy(3))('S(3)')] (2) and [Fe(CO)(dppe)('S(3)')] (3). The diastereoselective formation of 2 and 3 is rationalized by the trans influence of the 'S(3)'(2-) thiolate and thioether S atoms which act as pi donors and pi acceptors, respectively. The trans influence of the 'S(3)'(2-) sulfur donors also rationalizes the diastereoselective formation of the C(1) symmetrical anion of 4, when 1 is treated with four equivalents of NEt(4)CN. The molecular structures of 1, 3 x 0.5 C(7)H(8), and (AsPh(4))(2)[Fe(CN)(2)(CO)('S(3)')] x acetone (4 a x C(3)H(6)O) were determined by X-ray structure analyses. Complex 4 is the first complex that models the unusual 2:1 cyano/carbonyl and dithiolate coordination of the [NiFe] hydrogenase iron site. Complex 4 can be reversibly oxidized electrochemically; chemical oxidation of 4 by [Fe(Cp)(2)PF(6)], however, led to loss of the CO ligand and yielded only products, which could not be characterized. When dissolved in solvents of increasing proton activity (from CH(3)CN to buffered H(2)O), complex 4 exhibits drastic nu(CO) blue shifts of up to 44 cm(-1), and relatively small nu(CN) red shifts of approximately 10 cm(-1). The nu(CO) frequency of 4 in H(2)O (1973 cm(-1)) is higher than that of any hydrogenase state (1952 cm(-1)). In addition, the nu(CO) frequency shift of 4 in various solvents is larger than that of [NiFe] hydrogenase in its most reduced or oxidized state. These results demonstrate that complexes modeling properly the nu(CO) frequencies of [NiFe] hydrogenase probably need a [Ni(thiolate)(2)] unit. The results also demonstrate that the nu(CO) frequency of [Fe(CN)(2)(CO)(thiolate)(2)] complexes is more significantly shifted by changing the solvent than the nu(CO) frequency of [NiFe] hydrogenases by coupled-proton and electron-transfer reactions. The "iron-wheel" complex [Fe(6)[Fe('S(3)')(2)](6)] (6) resulting as a minor by-product from the recrystallization of 2 in boiling toluene could be characterized by X-ray structure analysis. 相似文献
3.
Summary Diphenyl(2-pyridyl)phosphine (PPh2pyl), phenylbis(2-pyridyl)-phosphine (PPhpyl2) and tris(2-pyridyl)-phosphine (Ppyl3) react with [Rh(acac)(CO)2] (acac=acetylacetonate) and Rh(8-oxy)(CO)2(8-oxy=8-hydroxyquinolinate) yielding [Rh(chel)(CO)(PPhxpyl3–x)]. The properties of these complexes were examined by spectral (i.r.,u.v.-vis,31P n.m.r.) and chemical methods. 相似文献
4.
The reaction of plutonium(IV) in aqueous nitric acid with tetra-n-butylammonium nitrate leads to the immediate precipitation of [N(n-Bu)(4)](2)[Pu(NO(3))(6)] (1) in high yield. The analogous reaction in HCl with tetra-n-butylammonium chloride gives [N(n-Bu)(4)](2)[PuCl(6)] (2). Both 1 and 2 are soluble in a range of organic solvents and have been characterized by single-crystal X-ray diffraction, IR spectroscopy, and solid- and solution-phase vis-near-IR spectroscopy. 1 and 2 provide facile synthetic entry routes to study plutonium(IV) ligand complexation reactions in organic solvent media under both air/moisture-stable and -sensitive conditions. 相似文献
5.
Calderoni F Demartin F Iapalucci MC Laschi F Longoni G Zanello P 《Inorganic chemistry》1996,35(4):898-905
A reinvestigation of the redox behavior of the [Fe(3)(&mgr;(3)-S)(CO)(9)](2)(-) dianion led to the isolation and characterization of the new [Fe(5)S(2)(CO)(14)](2)(-), as well as the known [Fe(6)S(6)(CO)(12)](2)(-) dianion. As a corollary, new syntheses of the [Fe(3)S(CO)(9)](2)(-) dianion are also reported. The [Fe(5)S(2)(CO)(14)](2)(-) dianion has been obtained by oxidative condensation of [Fe(3)S(CO)(9)](2)(-) induced by tropylium and Ag(I) salts or SCl(2), or more straightforwardly through the reaction of [Fe(4)(CO)(13)](2)(-) with SCl(2). The [Fe(6)S(6)(CO)(12)](2)(-) dianion has been isolated as a byproduct of the synthesis of [Fe(3)S(CO)(9)](2)(-) and [Fe(5)S(2)(CO)(14)](2)(-) or by reaction of [Fe(4)(CO)(13)](2)(-) with elemental sulfur. The structures of [N(PPh(3))(2)](2)[Fe(5)S(2)(CO)(14)] and [N(PPh(3))(2)](2)[Fe(6)S(6)(CO)(12)] were determined by single-crystal X-ray diffraction analyses. Crystal data: for [N(PPh(3))(2)](2)[Fe(5)S(2)(CO)(14)], monoclinic, space group P2(1)/c (No. 14), a = 24.060(5), b = 14.355(6), c = 23.898(13) ?, beta = 90.42(3) degrees, Z = 4; for [N(PPh(3))(2)](2)[Fe(6)S(6)(CO)(12)], monoclinic, space group C2/c (No. 15), a = 34.424(4), b = 14.081(2), c = 19.674(2) ?, beta = 115.72(1) degrees, Z = 4. The new [Fe(5)S(2)(CO)(14)](2)(-) dianion shows a "bow tie" arrangement of the five metal atoms. The two Fe(3) triangles sharing the central Fe atom are not coplanar and show a dihedral angle of 55.08(3) degrees. Each Fe(3) moiety is capped by a triply bridging sulfide ligand. The 14 carbonyl groups are all terminal; two are bonded to the unique central atom and three to each peripheral iron atom. Protonation of the [Fe(5)S(2)(CO)(14)](2)(-) dianion gives reversibly rise to the corresponding [HFe(5)S(2)(CO)(14)](-) monohydride derivative, which shows an (1)H-NMR signal at delta -21.7 ppm. Its further protonation results in decomposition to mixtures of Fe(2)S(2)(CO)(6) and Fe(3)S(2)(CO)(9), rather than formation of the expected H(2)Fe(5)S(2)(CO)(14) dihydride. Exhaustive reduction of [Fe(5)S(2)(CO)(14)](2)(-) with sodium diphenyl ketyl progressively leads to fragmentation into [Fe(3)S(CO)(9)](2)(-) and [Fe(CO)(4)](2)(-), whereas electrochemical, as well as chemical oxidation with silver or tropylium tetrafluoroborate, in dichloromethane, generates the corresponding [Fe(5)S(2)(CO)(14)](-) radical anion which exhibits an ESR signal at g = 2.067 at 200 K. The electrochemical studies also indicated the existence of a subsequent one-electron anodic oxidation which possesses features of chemical reversibility in dichloromethane but not in acetonitrile solution. A reexamination of the electrochemical behavior of the [Fe(3)S(CO)(9)](2)(-) dianion coupled with ESR monitoring enabled the spectroscopic characterization of the [Fe(3)S(CO)(9)](-) radical monoanion and demonstrated its direct involvement in the generation of the [Fe(5)S(2)(CO)(14)](n)()(-) (n = 0, 1, 2) system. 相似文献
6.
《Inorganic and Nuclear Chemistry Letters》1978,14(2-3):71-74
Alternative ways of obtaining metal-metal and metal-carbon bond energy terms, E(M-M) and E(M-C), from published thermochemical data for the clusters Rh4(CO)12 and Rh6(CO)16 are outlined. One gives average bond energy terms for the two clusters of E(M-M) = 86±11 and E(M-C) = 178±8 kJ.mol−1. The other, which makes allowance for the greater length, and presumably lower strength, of the metal-metal bonds of Rh6(CO)16, gives E(M-M) = 89±11 kJ.mol−1 for this cluster, 91±11 kJ.mol−1 for Rh4(CO)12, and E(M-C) = 175±8 kJ.mol−1. 相似文献
7.
The reaction of [Rh(4)(CO)(9)(mu-CO)(3)] with 3-hexyne to form the butterfly cluster [(mu(4)-eta(2)-3-hexyne)Rh(4)(CO)(8)(mu-CO)(2)] was monitored viain-situ Raman spectroscopy using an NIR laser source, at room temperature and under atmospheric argon using n-hexane as solvent. The collected raw spectra were deconvoluted using band-target entropy minimization (BTEM). The pure component mid-Raman spectra of the [Rh(4)(CO)(9)(mu-CO)(3)] and the butterfly cluster [(mu(4)-eta(2)-3-hexyne)Rh(4)(CO)(8)(mu-CO)(2)], were reconstructed with a high signal-to-noise ratio. Full geometric optimization and Raman vibrational prediction were carried out using DFT. The experimental and predicted Raman spectra were in good agreement. In particular, the far-Raman vibrational modes in the region 100-280 cm(-1) provided characterization of the metal-metal bonds and direct confirmation of the structural integrity of the polynuclear frameworks in solution. 相似文献
8.
9.
The reaction of [PPN](2)[Re(6)C(CO)(19)] with Mo(CO)(6) and Ru(3)(CO)(12) under sunlamp irradiation provided the new mixed-metal clusters [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] and [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)], which were isolated in yields of 85% and 61%, respectively. The compound [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] crystallizes in the monoclinic space group P2(1)/c with a = 20.190 (7) ?, b = 16.489 (7) ?, c = 27.778 (7) ?, beta = 101.48 (2) degrees, and Z = 4 (at T = -75 degrees C). The cluster anion is composed of a Re(6)C octahedral core with a face capped by a Mo(CO)(4) fragment. There are three terminal carbonyl ligands coordinated to each rhenium atom. The four carbonyl ligands on the molybdenum center are essentially terminal, with one pair of carbonyl ligands (C72-O72 and C74-O74) subtending a relatively large angle at molybdenum (C72-Mo-C74 = 147.2(9) degrees ), whereas the remaining pair of carbonyl ligands (C71-O71 and C73-O73) subtend a much smaller angle (C71-Mo-C73 = 100.5(9) degrees ). The (13)C NMR spectrum of (13)CO-enriched [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] shows signals for four sets of carbonyl ligands at -40 degrees C, consistent with the solid state structure, but the carbonyl ligands undergo complete scrambling at ambient temperature. The (13)C NMR spectrum of (13)CO-enriched [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)] at 20 degrees C is consistent with the expected structure of an octahedral Re(6)C(CO)(18) core capped by a Ru(CO)(3) fragment. The visible spectrum of [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] shows a broad, strong band at 670 nm (epsilon = 8100), whereas all of the absorptions of [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)] are at higher energy. An irreversible oxidation wave with E(p) at 0.34 V is observed for [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)], whereas two quasi-reversible oxidation waves with E(1/2) values of 0.21 and 0.61 V (vs Ag/AgCl) are observed for [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)]. The molybdenum cap in [Re(6)C(CO)(18)Mo(CO(4))](2-) is cleaved by heating in donor solvents, and by treatment with H(2), to give largely [H(2)Re(6)C(CO)(18)](2-). In contrast, [Re(6)C(CO)(18)Ru(CO)(3)](2-) shows no tendency to react under similar conditions. 相似文献
10.
Kevin Burgess Brian F.G. Johnson Jack Lewis Paul R. Raithby 《Journal of organometallic chemistry》1982,224(4):C40-C44
Organic azides [N3R] react with [Os3(CO)11(NCMe)] and with [Os3(μ-H)2(CO)10] to form [Os3(CO)10(NCMe)(N3COR)] (R Ph) and [Os3(μ-H)(CO)10(HN3R)] (R Ph, n-Bu, CH2Ph, cyclo-C6H11), respectively; the latter may be converted to [Os3(μ-H)2(CO)9(μ3-NR)] by thermolysis; the molecular structure of the phenyl derivative of each class of compound has been confirmed by x-ray analysis. 相似文献
11.
The coordination chemistry of 2,2'-dipyridyl diselenide (PySeSePy) (2) (C(10)H(8)N(2)Se(2)) has been investigated and its crystal structure has been determined (monoclinic, P2(1)/c, a = 10.129(2) ?, b = 5.7332(12) ?, c = 19.173(3) ?, beta = 101.493(8) degrees, Z = 4). In metal complexes the ligand was found to coordinate in three different modes, as also confirmed by X-ray structure determination. N,N'-coordination was found in the zinc complex [Zn(PySeSePy)Cl(2)] (3) (C(10)H(8)Cl(2)N(2)Se(2)Zn, triclinic, P&onemacr;, a = 7.9430(10) ?, b = 8.147(2) ?, c = 11.999(2) ?, alpha = 93.685(10) degrees, beta = 107.763(10) degrees, gamma = 115.440(10) degrees, Z = 2) and Se,Se'-coordination in the adduct of the ligand with bis(pentafluorophenyl)mercury(II) [PySeSePyHg(C(6)F(5))(2)] (5) (C(10)H(8)F(10)HgN(2)Se(2), monoclinic, P2(1)/n, a = 7.7325(10) ?, b = 5.9974(14) ?, c = 25.573, beta = 98.037(10) degrees, Z = 2), which however displays only weak interactions between selenium and mercury. The reaction of the ligand with norbornadiene carbonyl complexes of molybdenum and tungsten leads to reductive cleavage of the selenium-selenium bond with oxidation of the metal center and concomitant addition of the resulting selenolate to the metal carbonyl fragment. Thus the 7-coordinate complexes [Mo(SePy)(2)(CO)(3)] (6) (C(13)H(8)MoN(2)O(3)Se(2), monoclinic, P2(1)/n, a = 9.319(3) ?, b = 12.886(5) ?, c = 13.231(6) ?, beta = 109.23(3) degrees, Z = 4) and [W(SePy)(2)(CO)(3)] (7) (C(13)H(8)N(2)O(3)Se(2)W, monoclinic, P2(1)/n, a = 9.303(2) ?, b = 12.853(2) ?, c = 13.232(2) ?, beta = 109.270(10) degrees, Z = 4) were obtained. The same N,Se-coordination pattern emerges from the reaction of [Fe(2)(CO)(9)] with (2) leading to [Fe(SePy)(2)(CO)(2)] (8) (C(12)H(8)FeN(2)O(2)Se(2), monoclinic, P&onemacr;, a = 8.6691(14) ?, b = 12.443(2) ?, c = 14.085(2) ?, alpha = 105.811(10) degrees, beta = 107.533(8) degrees, gamma = 92.075(10) degrees, Z = 4). 相似文献
12.
Rhodium(I) complexes [Rh(TropNMe)(CO)(PPh3)] (TropNMe = 2-(N-methylamino)tropone, ONC8H9) (1) and [Rh(Trop)(CO)(PPh3)] · Acetone (Trop = Tropolone, O2C7H6) (2) have been synthesized and characterized by single-crystal X-ray diffraction analysis. A distorted square planar geometry about the rhodium(I) metal centre is observed in both compounds 1 and 2. Substitution of an oxygen atom with a methyl functionalized nitrogen atom does not significantly alter the bond distances and angles in the rhodium(I) complex. A theoretical study at B3LYP/6-31G(d) (main group) and LANL2DZ (Rh) level is presented to clarify the solid state behaviour of these complexes. 相似文献
13.
Alessandro Fumagalli Secondo Martinengo Gianfranco Ciani 《Journal of organometallic chemistry》1984,273(2):C46-C48
The new mixed PtRh cluster trianion [Pt2Rh9(CO)22]3? has been isolated as a minor product of the pyrolysis of [PtRh5(CO)15]?, and has been characterized by X-ray diffraction. The metal skeleton, which has ideal D3h symmetry, consists of three face-to-face condensed octahedra, as previously found in the isoelectronic species [Rh11CO)23]3?, with the Pt atoms on the three-fold axis, in the positions of maximum MM connectivity. 相似文献
14.
Summary The carbonyl ligands in the Rh1 complexes Rh(L-L)(CO)2 [L-L=anthranilate (AA) orN-phenylanthranilate(FA) ions] are replaced by P(OPh)3 to form the mono-or disubstituted products, Rh(L-L)(CO)[P(OPh)3] and Rh(L-L)[P(OPh)3]2 respectively depending on the [P(OPh)3]/[Rh] molar ratio, at room temperature and in air. Under argon at [P(OPh)3]/[Rh]4 theortho-metallated Rh1 complex Rh[P(OPh)3]3[P(OC6H4)-OPh)2] is formed. The new route forortho-metallated Rh1 complex synthesis is described.The Rh(AA)(CO)2 complex was used as a catalyst precursor in hydroformylation of olefins. 相似文献
15.
Setifi F Ouahab L Golhen S Hernandez O Miyazaki A Enoki T Toita T Yamada J Nishikawa H Łapiński A Swietlik R 《Inorganic chemistry》2002,41(14):3761-3768
The preparation, crystal structures, and optical and magnetic properties of two new charge-transfer salts kappa-(EDDH-TTP)(3)[Cr(phen)(NCS)(4)] x 2CH(2)Cl(2) (1) and kappa(21)-(BDH-TTP)(5)[Cr(phen)(NCS)(4)](2) x 2CH(2)Cl(2) (2), where phen = 1,10- phenanthroline, EDDH-TTP = 2-(4,5-ethylenedithio-1,3-dithiol-2-ylidene)-5-(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene, and BDH-TTP = 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene, are reported. Crystal data: (1) monoclinic P2(1)/a, a = 25.0752(5) A, b = 10.6732(3) A, c = 28.1601(6) A, beta = 95.195(2) degrees, Z = 4, R = 0.0585 for 6741 independent reflections with I > 3 sigma(I); (2) monoclinic P2(1)/a, a = 23.8275(4) A, b = 9.1015 (2) A, c = 27.0420(1) A, beta = 99.9297(8) degrees, Z = 4, R = 0.0530 for 4565 independent reflections with I > 2 sigma(I). The crystal structures for both compounds consist of alternating organic and inorganic layers. The organic layer in compound 1 is characterized as kappa-type, while the organic layer in 2 resembles the kappa-type but it contains orthogonal dimers and monomers, and it is therefore called kappa(21). Compound 1 shows metallic behavior down to low temperature. Salt 2 shows semiconductive behavior, which is explained as the result of either charge ordering owing to the kappa(21)-type structure or Peierls distortion due to the one-dimensional electronic nature. However, weak metallic behavior could be observed at 10 kbar above ca. 150 K and at 15 kbar above 170 K. The magnetic susceptibilities for both compounds show Curie-Weiss behavior, showing that the exchange interactions between the magnetic anions are weak. Polarized reflectance spectra of single crystals were measured over the spectral range from 650 to 7000 cm(-1). Moreover, absorption and diffusion reflectance spectra of powdered crystals dispersed in KBr (from 400 to 7000 cm(-1)) were recorded. Vibrational and electronic features are discussed. 相似文献
16.
The disproportionation of dicobalt octacarbonyl induced by the free carbene 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) and the X-ray characterization of the cyclohexane solvate of the resulting cobalt carbonyl N-heterocyclic carbene salt, [Co(CO)3(IMes)2]+[Co(CO)4]-.1/4C6H12, is reported. The crystal structure represents the first example of a [Co(CO)3(L)2][Co(CO)4] disproportionate salt reported to date. 相似文献
17.
Rambo JR Castro SL Folting K Bartley SL Heintz RA Christou G 《Inorganic chemistry》1996,35(23):6844-6852
Reactions of the previously reported dinuclear vanadium(III) thiolate anion [V(2)(edt)(4)](2)(-) (edtH(2) = ethane-1,2-dithiol) are described. Treatment of (NEt(4))(2)[V(2)(edt)(4)] (1) in MeCN with equimolar (C(12)H(8)S(2))BF(4) (C(12)H(8)S(2)(+) = the thianthrenium radical cation) results in a one-electron oxidation and isolation of the V(III),V(IV) complex (NEt(4))[V(2)(edt)(4)] (2). The same product can also be obtained by controlled-potential electrolysis of 1 at -0.20 V vs Ag/AgCl. Treatment of 1 in CH(2)Cl(2) with py gives no reaction, but addition of Me(3)SiCl leads to formation of the known V(2)OCl(4)(py)(6) (3). The latter is also formed by the reduction of a 1:1 mixture of VOCl(3) and VCl(3)(THF)(3) in CH(2)Cl(2)/py and by the reaction in CH(2)Cl(2) of VCl(3)(THF)(3) and py with edt(2)(-). Treatment of 1 in MeCN with bpy (2,2'-bipyridine) gives no reaction, but addition of Me(3)SiCl results in formation and isolation of [V(2)OCl(2)(bpy)(4)]Cl(2) (4) identified by spectroscopic comparison with literature data. The reaction of 1 in MeCN with equimolar VCl(3)(THF)(3) and NEt(4)Cl gives (NEt(4))(3)[V(3)Cl(6)(edt)(3)] (5). A more convenient procedure to 5 is the reaction in MeCN of VCl(3)(THF)(3), Na(2)edt, and NEt(4)Cl in a 1:1:1 molar ratio. Complex 5.MeCN crystallizes in triclinic space group P&onemacr; with (at -154 degrees C) a = 14.918(3) ?, b = 17.142(5) ?, c = 11.276(3) ?, alpha = 106.78(1) degrees, beta = 95.03(1) degrees, gamma = 106.18(1) degrees, and Z = 2. The anion contains a near-linear V(3) unit with a face-sharing trioctahedral structure: the three edt(2)(-) groups provide the six bridging S atoms; two edt(2)(-) groups are in a &mgr;-eta(2):eta(2) mode (as in 1), but the third is in a &mgr;(3)-eta(1):eta(2):eta(1) mode. The V.V separations (>3.1 ?) preclude V-V bonding. Variable-temperature solid-state magnetic susceptibility studies have been performed on complexes 1, 2, and 5 in a 1.0 kG field and 5.00-300 K temperature range. For 1, the effective magnetic moment (&mgr;(eff)) gradually decreases from 1.09 &mgr;(B) at 300 K to 0.26 &mgr;(B) at 5.00 K. The data were fit to the Bleaney-Bowers equation, and the fitting parameters were J = -419(11) cm(-)(1) and g = 2.05. The singlet-triplet gap is thus 838 cm(-)(1). For 2, &mgr;(eff) is essentially temperature-independent, slowly decreasing from 1.90 &mgr;(B) at 300 K to 1.86 &mgr;(B) at 55 K and then to 1.63 &mgr;(B) at 5.00 K. The complex thus is S = (1)/(2) with no thermally accessible S = (3)/(2) state. The combined data on 1 and 2, together with the results of EHT calculations, show that 1 and 2 contain a V-V single bond tying up two of the d electrons and that the remaining two d electrons in 1 are antiferromagnetically coupled to give an S = 0 ground state and S = 1 excited state; for 2, the one remaining d electron gives an S = (1)/(2) state. For 5, &mgr;(eff) increases from 5.17 &mgr;(B) at 320 K to a maximum of 6.14 &mgr;(B) at 30.0 K and then decreases slightly to 6.08 &mgr;(B) at 5.00 K. The data were fit to the appropriate theoretical expression to give J = +42.5(6) cm(-)(1), J' = -1.8(5) cm(-)(1), and g = 1.77, where J and J' gauge the interactions between adjacent and terminal V(III) atoms, respectively. The complex has an S = 3 ground state and represents a very rare example of ferromagnetic coupling between V(III) centers. 相似文献
18.
19.
Yu.S. Varshavsky M.R. Galding S.N. Smirnov 《Journal of organometallic chemistry》2007,692(26):5788-5794
Selective oxidation of one (trans to N) carbonyl group in [Rh(8-Oxiquinolinato)(CO)2] with stoichiometric amount of Me3NO in MeCN produces a solution containing [Rh(Oxq)(CO)(Me3N)] and [Rh(Oxq)(CO)(MeCN)]. The ammonia complex, [Rh(Oxq)(CO)(NH3)], has been prepared by action of NH3 gas on this solution and characterized by IR, 1H and 13C NMR, and X-ray data. Spectral parameters, ν(CO), δ13C, and 1J(CRh), were measured in situ for a series of complexes [Rh(Oxq)(CO)(L)] (L = NAlk3, Py, PBu3, PPh3, P(OPh)3, C8H14) formed upon action of L on [Rh(Oxq)(CO)(NH3)] in THF. A new ν(CO) and δ13C based scale of σ-donor/π-acceptor properties of ligands L is proposed including NH3 and CO as the natural endpoints. 相似文献
20.
Synthese und Kristallstrukturen von (NEt4)2[TeS3], (NEt4)2[Te(S5)(S7)] und (NEt4)4[Te(S5)2][Te(S7)2]
Synthesis and Crystal Structures of (NEt4)2[TeS3], (NEt4)2[Te(S5)(S7)], and (NEt4)4[Te(S5)2][Te(S7)2] (NEt4)2[TeS3] was obtained by the reaction of NEt4Cl, Na2S4 and tellurium in acetonitrile. It reacts with sulfur, yielding (NEt4)2[Te(S5)(S7)], which is transformed to (NEt4)4[Te(S5)2][Te(S7)2] by recrystallization from hot acetonitrile. According to the X-ray structure analysis, crystals of (NEt4)2[TeS3] are monoclinic (space group P21/c) and form twins with the twinning plane (001); they contain pyramidal TeS32– ions. (NEt4)2[Te(S5)(S7)] forms triclinic twins (space group P1) with the twinning plane (010). In the [Te(S5)(S7)]2– ion an S5 and an S7 atom group are bonded in a chelate manner to the tellurium atom, which has square coordination. (NEt4)4[Te(S5)2][Te(S7)2] (monoclinic, space group P21/c) contains two kinds of anions, the known [Te(S5)2]2– and the new [Te(S7)2]2– ion which has two S7 chelating groups. 相似文献