Nitrosyl complexes of technetium: synthesis and characterization of TcI(NO)(CNCMe3)52 and Tc(NO)Br2(CNCMe3)3 and the crystal structure of Tc(NO)Br2(CNCMe3)3 (original) (raw)
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Eur. J. Inorg. Chem. 2005, 879
Keywords: Cobalt(ii) cubanes / Dicyanamide complexes / Di-2-pyridyl ketone / Magnetic properties / Manganese (ii) cubanes / Nickel(ii) cubanes The use of di-2-pyridyl ketone [(2-py) 2 CO]/dicyanamide "blend" in cobalt(II), manganese(II) and nickel acetate chemistry has yielded neutral cubane clusters. The preparation of [Mn 4 (O 2 CMe) 2 {N(CN) 2 } 2 {(2-py) 2 C(OH)O} 4 ]·2(2-py) 2 -CO·4H 2 O (1) and [M 4 (O 2 CMe) 2 {N(CN) 2 } 2 {(2-py) 2 C(OH) O} 4 ]·10H 2 O [M = Ni (2), Co (3)] was achieved by the reaction of [M(O 2 CMe) 2 ]·4H 2 O with (2-py) 2 CO and Na[N(CN) 2 ] in MeOH/H 2 O (1:5, v/v) at room temperature. The metal(II)-mediated hydrolysis of (2-py) 2 CO to give the coordinated monoanion of the hydrate gem-diol form involves a nucleophilic attack of H 2 O on the carbonyl group. In the case of the cobalt reaction system, there is a second product. Upon employing an excess of (2-py) 2 CO, long reaction times, reflux conditions and high dilution, slow oxidation of Co II takes place leading to the isolation of the mononuclear cobalt(III) complex [Co{(2-py) 2 C(OH)O} 2 ][N(CN) 2 ]·4H 2 O (4) in yields higher than 70 %. The structures of 1, 2 and 4 have been solved by single-crystal X-ray diffraction studies, while a [a] www.eurjic.org Eur. J. Inorg. Chem. 2005, 879-893 880 1: M = Mn II , n = 2, m = 4 2: M = Ni II , n = 0, m = 10 3: M = Co II , n = 0, m = 10 www.eurjic.org Eur. J. Inorg. Chem. 2005, 879-893 882 distance of 2.289 Å, whereas the two other bonds are shorter (average distance 2.179 Å). The cube deviates from the ideal geometry. The internal cube angles (RO-Mn-OR) at the metal vertices average 79.4°, whereas the comparable Eur.
The reactions of di-2-pyridyl ketone with Cu(O 2 CPh) 2 in the presence of NaN 3 and LiOH have led to an antiferromagnetically coupled (S ) 0) Cu II 6 cluster with a novel core and to (Cu II 8 ) n and (Cu II 2 ) n coordination polymers (the former 1D and the latter 2D) with interesting structures. The cluster or polymer formation depends on the reaction solvent.
Comments Inorg. Chem. 2002, 249
The synthetic and structural chemistry of polynuclear manganese, cobalt, nickel and copper carboxylate complexes, stabilized by various forms of di-2-pyridyl ketone, is discussed. The structural diversity displayed by the described complexes stems from the ability of the doubly and singly deprotonated forms of the gem-diol form of di-2-pyridyl ketone, or the monoanion of the hemiacetal form of this ligand, to adopt a variety of coordination modes. The nuclearities of the clusters vary from four to fourteen. Perhaps the most aesthetically pleasing families are the ''flywheel Cu 12 clusters, and the Co 9 and Ni 9 complexes in which the nine metal ions adopt a topology of two square pyramids sharing a common apex. A means of increasing the ground-state total spin value of a polynuclear 3d-metal cluster is also proposed. The approach is based on the replacement of hydroxo bridges, that most often propagate antiferromagnetic exchange interactions in clusters, by the end-on azido ligand, which is a well known ferromagnetic coupler. This approach involves ''true'' reactivity chemistry on pre-isolated clusters and the products are not undergone significant structural changes, except for the azido-for-hydroxo substitution, compared to the starting materials/ clusters.
Inorg. Chem. Front., 2015,.pdf
A potential tetradentate monoanionic N 2 O 2 chelator, HL, derived from the condensation of o-vanillin and N,N-dimethylethylenediammine, has been reacted with nickel perchlorate and sodium azide to yield the dinuclear Ni(II) complex [Ni(L)(μ 1,1 -N 3 )Ni(L)(OH 2 ) 2 ]·ClO 4 (1), where L = Me 2 N(CH 2 ) 2 NvCH-C 6 H 3 (O − )-(OCH 3 ). The complex has been characterized by X-ray diffraction analysis and different spectroscopic techniques. The coordination geometry around the Ni(II) centres is a distorted octahedron, with the azide ligand and the phenolato oxygen atom bridging in μ 1,1 and μ 2 mode, respectively. The EPR spectra, recorded at liquid nitrogen temperature (77 K) and room temperature ), show g factors of 2.080 and 2.085, in agreement with the structure determined by X-ray diffraction analysis. The VTM study confirms that there are ferromagnetic interactions between the bridging binuclear Ni(II) ions (S = 1). The evaluation of cytotoxic effects on different human cancer cell lines (A-549, MCF-7 and CaCo-2) suggests that both the ligand and complex 1 have potential anticancer properties. Furthermore, they also exhibit anti-mycobacterial activity against M. tuberculosis H37Rv (ATCC 27294) and M. tuberculosis H37Ra (ATCC 25177) strains. Molecular docking of HL with the enoyl acyl carrier protein reductase of M. tuberculosis H37R v (PDB ID: 4U0K) has been examined, showing that HL forms two hydrogen bonds with Lys165 (1.94 and 2.53 Å) in its best docked pose. † Electronic supplementary information (ESI) available. CCDC 894363. For ESI and crystallographic data in CIF or other electronic format see
Nazira Mukhanbetova Lecture Notes in General and Inorganic Chemistry Part 2
Lecture Notes in General and Inorganic Chemistry Part 2, 2017
In second part of Lecture notes in General and Inorganic Chemistry provides an introduction to the chemistry of inorganic molecules. The emphasis is on basic principles of electrochemistry, redox equilibria, electrolysis and corrosion, properties of important metals and nonmetals. Written primarily for use as a textbook for a university-level course, the topics covered here provide the fundamental tools necessary for an accomplished engineer.
Inorganic Chemistry, 1980
protons is lost upon oxidation. The title complex is further characterized by the reactivity patterns which it displays. For example, both [(en),Co(SC-(O)COO)]+ and [(en)zCo(SC(0)C(O)S)]+ undergo rapid base hydrolysis to yield H2S, cobalt(II), and free oxalate. Both complexes also undergo acid hydrolysis and yield H2S and oxalic acid on heating in ca. 6 M acid. In addition, [(en),Co(SC(O)COO)]+ is much more resistant to oxidation than [(en)2Co(SCH2C00)]+, but it can be oxidized under stringent conditions (e.g., by using silver-catalyzed persulfate). Structural parameters observed for [(en),Co(SC(O)C0O)],(S2O6) (Tables VI and VII) are in reasonable agreement with those obtained by Gainsford, Jackson, and S a r g e~o n~~ in a study of the analogous chloride salt. In general, the structure of the [(en),Co(SC(O)COO)]+ cation is as expected from the known structure of the parent thiolato complex [(en)zCo(SCH2C00)]+.3 However, the structural trans effect (STE) induced by the coordinated sulfur atom is significantly smaller3' for the thiooxalato com lex than Crystal Structure. for the thiolato complex (0.005 (8) vs. 0.043 (5) 8:). This (37) Sargeson32 also finds the shortest Cc-N bond to be that trans to 0. The sulfur STE computed from his data for the chloride salt is 0.018 (3) A. result is in harmony with the hypothesis that charge donation from sulfur to cobalt(II1) is the underlying cause of the STE.34 The electron-withdrawing effect of the adjacent carbonyl in thiooxalate reduces the tendency of the sulfur atom of this ligand to donate electron density (relative to the sulfur atom of the parent thiolato ligand). This result allows us to extend the previously noted34 STE series for cobalt(II1): S032-> RSO-> RS02-> RS-> S2O3'-N RSR N RC(0)S-. Acknowledgment. Financial support by the National Science Foundation, Grants No. C H E 76-19681 and C H E 79-26497, is gratefully acknowledged. Registry No. [(en)2Co(SC(0)COO)]2(S206)~2H20, 73612-1 1-0; [ (en)2Co(SC(0)COO)]Cl, 736 12-1 2-1 ; [ (en)2Co(SC(0)COO)]C104, 7361 2-1 3-2; [(en)2Co(00CC00)]f, 17835-7 1-1 ; [(en)2Co(SC(0)-COO)]', 736 12-09-6; [ (en),Co(SC(O)C(O)S)]+, 73650-78-9; [(en)2Co(SCH2C00)]C1, 54453-35-9; [(en)2Co(OOCCOO)]Cl, 17439-00-8; [ (en)2Co(SC(0)C(O)S)] C1, 14267-1 2-0; [ (en)*Co-(SCH2C00)]C104, 26743-67-9; cis-[(en),CoCI2]C1, 14040-32-5. Supplementary Material Available: Tables A-C giving lFol and F,, anisotropic thermal parameters, and positional parameters of hydrogen atoms (9 pages). Ordering information is given on any current masthead page.