The neutral dinuclear iron nitrosyl complex [Fe2(SC3H5N2)2(NO)4] (1) of the “g = 2.03” family with a ligand analogous to natural mercaptohistidine was synthesized by the metathesis reaction
of the thiosulfate ligands in the [Fe2(S2O3)2(NO)4]2− anion with imidazolidine-2-thiolate ligands. The electrochemical determination of nitrogen oxide in solution showed that
compound 1 has a lower NO-donor ability compared to the iron complexes with 1-methylimidazole-2-thiol and imidazole-2-thiol synthesized
earlier. Study of the magnetic properties of polycrystals of 1 demonstrated that the effective magnetic moment at room temperature is ca. 2.45 μB and corresponds to a molecule containing a pair of the noninteracting spins S = 1/2. This is evidence that each iron coordination
unit in complex 1 contains one unpaired electron, and the iron atom is in the low-spin state.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 28–34, January, 2007. 相似文献
The reaction of rhenium α-diimine (N-N) tricarbonyl complexes with nitrosonium tetrafluoroborate yields the corresponding dicarbonyl-nitrosyl [Re(CO)2(NO)(N-N)X]+ species (where X = halide). The complexes, accessible in a single step in good yield, are structurally nearly identical higher charge congeners of the tricarbonyl molecules. Substitution chemistry aimed at the realization of equivalent dicationic species (intended for applications as potential antimicrobial agents), revealed that the reactivity of metal ion in [Re(CO)2(NO)(N-N)X]+ is that of a hard Re acid, probably due to the stronger π-acceptor properties of NO+ as compared to those of CO. The metal ion thus shows great affinity for π-basic ligands, which are consequently difficult to replace by, e.g., σ-donor or weak π-acids like pyridine. Attempts of direct nitrosylation of α-diimine fac-[Re(CO)3]+ complexes bearing π-basic OR-type ligands gave the [Re(CO)2(NO)(N-N)(BF4)][BF4] salt as the only product in good yield, featuring a stable Re-FBF3 bond. The solid state crystal structure of nearly all molecules presented could be elucidated. A fundamental consequence of the chemistry of [Re(CO)2(NO)(N-N)X]+ complexes, it that the same can be photo-activated towards CO release and represent an entirely new class of photoCORMs. 相似文献
The title complex has the NO grouptrans to the hydroxyl ligand and the chloride ion in the plane of the tripyridyl ligand. The Ru−O and Ru−N(O) distances are 1.939(5)
? and 1.764(6) ?, respectively; the Ru−N−O bond angle is 171.7(6)0. These values are consistent with previously reported shortening of Ru−O distances whentrans to a linear NO ligand. The space group of the structure isP21/c, witha=9.7213(9) ?,b=13.9318(11) ?,c=14.523(4) ?, and β=105.820(13)0. 相似文献
Symmetrically disubstituted bis(3-hydroxyalkynyl) complex [TpRu{C[triple chemical bond]CCPh(2)(OH)}(2)(NO)] (1) (Tp = BH(pyrazol-1-yl)(3)) and unsymmetrically mixed (arylalkynyl)(3-hydroxyalkynyl) congener [TpRu(C[triple chemical bond]CC(6)H(4)Me){C[triple chemical bond]CCPh(2)(OH)}(NO)] (2) were newly prepared. Treatment of 1 or 2 with p-toluenesulfonic acid monohydrate was carried out to give unusual four-membered metallacyclic complexes [TpRu{C(=C=CPh(2))C(O)C(=CPh(2))}(NO)] (3) and [TpRu{C(=C=CPh(2))C(O)CH(C(6)H(4)Me)}(NO)] (5), respectively, as major products. Formation mechanism of 3 and 5 would involve insertion of the generated allenylidene group (Ru=C=C=CPh(2)) into the other Ru--C(alkynyl) bond, followed by hydration of the resulting alpha-alkynyl--allenyl fragment. With regards to the chemical reactivity of their four-membered metallacycles, treatment with aq. HCl in MeOH afforded the ring-opened one-HCl adducts, [TpRuCl{C(=C=CPh(2))C(O)CH=CPh(2)}(NO)] (7) and [TpRuCl{C(=C=CPh(2))C(O)CH(2)(C(6)H(4)Me)}(NO)] (8). On the other hand, the use of CH(2)Cl(2) and THF as the reaction solvent gave another type of one-HCl adducts [TpRu{CH(C(Cl)=CPh(2))C(O)C(==CPh(2))}(NO)] (9 a/9 b) and [TpRu{CH(C(Cl)=CPh(2))C(O)CH(C(6)H(4)Me)}(NO)] (11 a/11 b) as diastereomeric pairs, still retaining the four-membered ring structure. Moreover, their kinetically controlled products 9 b and 11 b were treated with aq. HCl to afford the ring-opened two-HCl adducts [TpRuCl{C(C(Cl)=CPh(2))(H)C(O)CH=CPh(2)}(NO)] (10) and [TpRuCl{CH(C(6)H(4)Me)C(O)CH(2)(C(Cl)=CPh(2))}(NO)] (12), respectively. In 10 and 12, each one Ru--C bond is cleaved at mutually different positions in the ring. Protonation on the carbonyl group would trigger the formation of 7-12. 相似文献
[(TMEDA)Co(NO)2][BPh4] reacts with Group 1 salts of various monoanionic ligands to yield four and five coordinate {Co(NO)2}10 complexes. The synthesis of the four coordinate complex of the form [{LX}Co(NO)2] via salt-metathesis reactions of [(TMEDA)Co(NO)2][BPh4] with [{ArNC(Me)CHC(Me)NAr}Li(OEt2)] (Ar = 2,6-di-iso-propylphenyl) is reported. In addition [(TMEDA)Co(NO)2][BPh4] reacts with either KTp∗ or a suite of cyclopentadienyllithium and cyclopentadienylsodium reagents, to generate the corresponding five coordinate [{L2X}Co(NO)2] complexes ({L2X = C5H5, MeC5H4, Cp∗, tBuC5H4, Ph2CHC5H4, Me3SiC5H4, tBuMe2SiC5H4, iPr3SiC5H4, 1,3-(iPr3Si)2C5H3 and Tp∗). In support of existing precedent, the four coordinate complex is a thermally robust and readily isolable species while five coordinate complexes are thermally unstable transient intermediates that may either undergo dissociation of an NO ligand or be trapped by alkenes to form the corresponding metal dinitrosoalkane complexes. These reactions demonstrate that [(TMEDA)Co(NO)2][BPh4] provides a versatile synthetic entry point to cobalt dinitrosyl complexes and obviates the need for the repeated use of nitric oxide in the preparation of dinitrosoalkane complexes of cobalt. 相似文献
A cyano-bridged heterometallic lanthanide-transition metal nitrosyl complex, [Pr(phen)2(MeOH)(H2O)2][Fe(CN)5(NO)]?·?(Phen)(DMF)(MeOH)(H2O) (Phen?=?1,10-phenanthroline and DMF?=?dimethylformamide), has been synthesized from reaction of PrCl3?·?6H2O with 1,10-phenanthroline in methanol and sodium nitroprusside followed by crystallization from DMF. The crystal structure shows that the complex is a 1-D chain, stabilized by coordination, hydrogen-bonding, and π–π stacking interactions. The complex shows nuclease activity with pUC19 supercoiled DNA in DMF/Tris-HCl buffer in the presence of H2O2. 相似文献
The iron dithiolene compounds [Fe2(mnt)4]2− [1]2− and [Fe(NO)(mnt)2]n (n = 1−, [2]1−; n = 2−, [2]2−) ([mnt]2− = maleonitriledithiolate = [(NC)2C2S2]2−) have been characterized structurally by X-ray diffraction as their [Et4N]+ salts at 100 K. Dianion [2]2− is prepared from [2]1− by reduction with Na[Et3BH] and is observed to have a bent Fe-NO angle at 149.9(5)° in contrast to the linear configuration of Fe-NO in [2]1− (180.0°). The change from linear to bent binding mode for NO, an increase of more than 0.1 Å in the Fe-N bond length, and the relative invariance of the Fe-S distances for [2]2− versus [2]1− indicate that the NO ligand is the site of reduction. The [Et3NH]+ complex of [2]1− was also identified by crystallography and found to have hydrogen bonding contacts between [Et3NH]+ and the cyano nitrogen atom of an [mnt]2− ligand. Furthermore, relatively close S?S contacts (3.602-3.615 Å) occur between [2]1− anions, which pack together in an offset, head-to-head fashion. These S?S contacts are absent in the structure of [Et4N][2]. Infrared spectra show an energy decrease for, and a significant broadening of, the NO bond stretching absorption peak in [2]2−, which is consistent with a bent NO ligand sampling a range of conformations both by facile pivoting about the Fe-N axis and by a breathing of the Fe-NO angle. 相似文献
Abstract Instigated by developing a flow injection procedure for assay of nitrosyl in concentrated sulphuric acid, different approaches for reliable and robust on-line dilution in FIA were evaluated. These comprised the application of mixing tees in conjunction with mixing coils (including knotted reactors) of different internal diameter, zone sampling, the use of a mixing chamber, micro-sampling, and sample injection by means of pseudo-hydrodynamic injection. The individual approaches are described in detail, their advantages and disadvantages being emphasized in regard to their practical applicability. For each approach the criteria stipulated were that the procedure should allow a dilution factor of approximately 100, yet without excessive zone spreading, so that it, on one hand, could effectively eliminate the pronounced Schlieren effect encountered when mixing concentrated sulphuric acid with an aqueous diluent, and, on the other hand, would permit the sample material to be appropriately conditioned for the ensuing chemical derivatization procedure. It was found that this most reliably could be effected by a combination of pseudo-hydrodynamic injection comprising a mixing point and the use of mixing tees in conjunction with knotted reactors of relatively large internal diameter (1.5 mm). The optimized FI-manifold was used with the Griess method for the spectrophotometric assay of nitrosyl (nitrite) in standards prepared in the matrix of concentrated sulphuric acid (detection limit 0.16 mg/1 NO+-N (3[sgrave])) and in practical WSA-samples. 相似文献
Six combinations of oxidation states are conceivable for the paramagnetic title complex. Single‐crystal X‐ray diffraction, spectroscopic analysis (IR, EPR at conventional and high frequency), and DFT calculations establish that it is the iminosemiquinone radical structure that is formed: [Ruk(NOm)(Qn)(terpy)]2+ (k=2+, m=1+, n=1?).