15496-36-3Relevant articles and documents
Mononuclear, dinuclear, and pentanuclear [{N,S(thiolate)}iron(II)] complexes: Nuclearity control, incorporation of hydroxide bridging ligands, and magnetic behavior
Krishnamurthy, Divya,Sarjeant, Amy N.,Goldberg, David P.,Caneschi, Andrea,Totti, Federico,Zakharov, Lev N.,Rheingold, Arnold L.
, p. 7328 - 7341 (2005)
The mixed N3S(thiolate) ligand 1-[bis(2-(pyridin-2-yl)ethyl} amino]-2-methylpropane-2-thiol (Py2SH) was used in the synthesis of four iron(II) complexes: [(Py2S)FeCl] (1), [(Py2S)FeBr] (2), [(Py2S)4Fe5II(μ-OH) 2]-(BF4)4 (3). and [(Py2S) 2Fe2II(μ-OH)]BF4 (4). The X-ray structures of 1 and 2 revealed monomeric iron(II)-alkylthiolate complexes with distorted trigonal-bi-pyramidal geometries. The paramagnetic 1H NMR spectra of 1 and 2 display resonances from δ = -25 ppm to + 100 ppm, consistent with a high-spin iron(II) ion (S=2). Spectral assignments were made on the basis of chemical shift information and T1 measurements and show the monomeric structures are intact in solution. To provide entry into hydroxide-containing complexes, a novel synthetic method was developed involving strict aprotic conditions and limiting amounts of H2O. Reaction of Py2SH with NaH and Fe-(BF4)2·6H 2O under aprotic conditions led to the isolation of the pentanuclear, μ-OH complex 3, which has a novel dimer-of-dimers type structure connected by a central iron atom. Conductivity data on 3 show this structure is retained in CH2Cl2. Rational modification of the ligand-to-metal ratio allows control over the nuclearity of the product, yielding the dinuclear complex 4. The X-ray structure of 4 reveals an unprecedented face-sharing, biooctahedral complex with an [S2O] bridging arrangement. The magnetic properties of 3 and 4 in the range 1.9-300 K were successfully modeled. Dinuclear 4 is antiferromagnetically coupled [J = -18.8(2) cm-1]. Pentanuclear 3 exhibits ferrimagnetic behavior, with a high-spin ground state of ST=6, and was best modeled with three different exchange parameters [J= -15.3(2), J′ = -24.7(3), and J″ = -5.36(7) cm-1]. DFT calculations provided good support for the interpretation of the magnetic properties.
Dioxygen mediated oxo-transfer to an amine and oxidative N-dealkylation chemistry with a dinuclear copper complex
Zhang,Liang,Kim,Gan,Tyeklar,Lam,Rheingold,Kaderli,Zuberbuehler,Karlin
, p. 631 - 632 (2007/10/03)
Reaction of dioxygen with a dinuclear copper(I) complex of a new binucleating ligand is described, wherein a peroxodicopper(II) (Cu2-O2) intermediate leads to an oxo-transfer reaction to give an N-oxide of an N-benzyl internal ligand
SYNTHESIS OF FUNCTIONALLY SUBSTITUTED PYRIDINES AND DIPYRIDYL-SUBSTITUTED COMPOUNDS WITH THE AID OF LOW-VALENCE COMPOLEXES
Selimov, F. A.,Khafizov, V. R.,Dzhemilev, U. M.
, p. 290 - 295 (2007/10/02)
The possibility of the preparation of oxygen, nitrogen, and sulfur-containing pyridines and dipyridyl-substituted compounds by the cyclocotrimerization of substituted propionitriles with acetylene under the influence of a Co(2-ethylhexanoate)2-Al(C2H5)3 catalyst was demonstrated.It was established that the nature of the heteroatom in substituted propionitriles has virtually no effect on the direction of the reaction.
