Switching from a Chromium(IV) Peroxide to a Chromium(III) Superoxide upon Coordination of a Donor in the trans Position

2019 ◽  
Vol 141 (36) ◽  
pp. 14068-14072 ◽  
Author(s):  
Marie-Louise Wind ◽  
Santina Hoof ◽  
Beatrice Braun-Cula ◽  
Christian Herwig ◽  
Christian Limberg
Keyword(s):  
2005 ◽  
Vol 70 (8-9) ◽  
pp. 1121-1129 ◽  
Author(s):  
Gordana Vuckovic ◽  
V. Stanic ◽  
Sofija Sovilj ◽  
M. Antonijevic-Nikolic ◽  
J. Mrozynski

Novel binuclear Co(II) complexeswithN-functionalized cyclam N,N?,N",N???-tetrakis( 2-pyridylmethyl)tetraazacyclotetradecane (tpmc) and one of the aromatic monoor dicarboxylato ligands (benzoate, phthalate or isophthalate ions) were prepared. They were analyzed and studied by elemental analyses (C, H, N), electrical conductivities, VIS and IR spectroscopy andmagnetic as well as cyclic voltammetric measurements. In [Co2(C6H5COO)2tpmc]ClO4)2.3H2O, the benzoate ligands are most probably coordinated as chelates in the trans-position to each Co(II) and the macrocycle adopts a chair conformation. In the complexes [Co2(Y)tpmc]ClO4)2.zH2O, (Y = phthalate or i-phthalate dianizon, z = 2; 4) it is proposed that the isomeric dicarboxylates are bonded combined as bridges and chelates. The composition and the assumed geometries of the complexes are compared with the, earlier reported, corresponding Cu(II) complexes. Cyclic voltammetry measurements showed that the compounds are electrochemically stable.


1987 ◽  
Vol 42 (11) ◽  
pp. 1398-1402 ◽  
Author(s):  
Dieter Fenske ◽  
Karin Völp ◽  
Kurt Dehnicke

MoF4(NCl) has been prepared as a yellow crystal powder by the reaction of diluted fluorine with MoCl3(N3S2) at room temperature. The compound is associated via fluorine bridges, according to the IR spectrum. With acetonitrile, the monomeric complex [CH3CN -MoF4(NCl)] is obtained, which was characterized by its IR and 19F NMR spectra as well as by an X-ray structure determination. Crystal data: space group Pm, Z = 2 (1068 observed, independent reflexions, R = 0.03). Lattice dimensions at -90 °C: a = 507.1. b = 704.8, c = 995.8 pm, β = 102.02°. The unit cell contains two crystallographically independent molecules [CH3CN -MoF4(NCl)], the Mo≡N-Cl groups being linear (bond angles 176°, 178°) with bond lengths MoN = 172 and NCI = 159, 162 pm. In the trans position to the MoNCl group, the nitrogen atom of the acetonitrile molecule is coordinated.


1993 ◽  
Vol 48 (12) ◽  
pp. 1841-1844 ◽  
Author(s):  
Eva Rentschler ◽  
Kurt Dehnicke

The complexes [MoNCl3·DME] and [WNCl3·DME] (DME = 1,2-dimethoxyethane) have been prepared by the reaction of the nitride chlorides MNC13 with equimolar amounts of DME in CH2Cl2 suspensions. They form orangered, moisture sensitive crystals, which are soluble in organic solvents. The molybdenum complex has been characterized by a crystal structure determination. Space group Pbca, Z = 8, structure solution with 1781 observed unique reflections, R = 0.031. Lattice dimensions at –60°C: a = 738.6(1), b = 1182.2(1), c = 2314.1(1) pm. [MoNCl3·DME] forms monomeric complexes with chelating DME molecules and Mo–O bond lengths of 215.4(4) and 247.4(4) pm, the longer one being in trans-position of the nitrido ligand. The MoN bond length of 163.3(5) pm suggests a triple bond.


1984 ◽  
Vol 39 (8) ◽  
pp. 1114-1117 ◽  
Author(s):  
Willi Kafitz ◽  
Kurt Dehnicke ◽  
Eberhard Schweda ◽  
Joachim Strähle

AbstractReNF4 · ReF5(NCl) is prepared by direct fluorination of ReNCl4 with fluorine between 80 °C and 130 °C. The red crystals are extremely sensitive to moisture. The complex is characterized by the IR spectrum and by an X-ray structural investigation. ReNF4 · ReF5(NCl) crystallizes orthorhombically in the space group Pnma with 4 formula units per unit cell and with the cell dimensions a = 1440, b = 848, c = 776 pm (419 observed, independent reflexions, R = 13.9%). The complex consists of the molecules ReNF4 and ReF5(NCl), which are linked by a linear asymmetric fluorine bridge. The bridging fluorine atom is in trans-position to the nitrido ligand Re -F - 228 pm) and to the nitreno ligand (Re -F = 159 pm and Re= N - Cl 164 pm) correspond to triple 188 pm). The Re ≡ N bond lengths Re= N bonds.


1972 ◽  
Vol 115 (1) ◽  
pp. 19-25
Author(s):  
R. Kolstad ◽  
L. Enquist

1989 ◽  
Vol 44 (8) ◽  
pp. 889-892 ◽  
Author(s):  
John David Kildea ◽  
Wolfgang Hiller ◽  
Beatrice Borgsen ◽  
Kurt Dehnicke

The title compound [Na(15-crown-5)][C6H5–C(NSiMe3)2SnCl3F] is synthesized by the reaction of sodium fluoride with Ph—C(NSiMe3)2SnCl3 in acetonitrile solution in the presence of 15-crown-5 as white, moisture-sensitive crystals. The complex is characterized by its IR spectrum as well as by an X-ray structure determination. Space group P212121 Z = 4, 4897 observed independent reflexions, R = 0.094. Lattice dimensions at 20°C: a = 1065.7(2), b = 1431.0(2), c = 2325.6(3) pm. The compound forms ion pairs with a bent Sn–F–Na bridge (bonding angle 119.0(5)°) and distances Sn–F of 196(1) and Na–F of 232(1) pm. The tin atom is in a distorted octahedral environment defined by the two N atoms of the symmetrically coordinated amidinato ligand, by three chlorine atoms, and by the fluorine ligand; the latter is in a trans-position relative to one of the nitrogen atoms.


2016 ◽  
Vol 45 (37) ◽  
pp. 14801-14813 ◽  
Author(s):  
Svea Hinrichsen ◽  
Ann-Christin Schnoor ◽  
Katharina Grund ◽  
Benedikt Flöser ◽  
Alexander Schlimm ◽  
...  

The syntheses of new molybdenum dinitrogen complexes supported by the tridentate PEP ligands (E = N, P) prPP(Ph)P (2), prPPHP (3), PN(Ph)P (4) and prPN(Ph)P (5) are reported.


1996 ◽  
Vol 51 (8) ◽  
pp. 1111-1116 ◽  
Author(s):  
Abdel-Fattah Shihada ◽  
Frank Weller

Et2Sn(O2PPh2)2 has been synthesized by the reaction of (Et2ClSn)2O with Ph2POCl in toluene and by the treatment of (Et2ClSn)2O or Et2SnCl2 with HO2PPh2 in methanol. The reaction of Et2SnO with HO2PMe2 in toluene was used to prepare Et2Sn(O2PMe2)2. An X-ray diffraction study of Et2Sn(O2PPh2)2 (space group P1̅, Z = 1, a = 559,9( 1), b = 983,7(1), c = 1262,4(l)pm, α = 81,85( 1 )°, β = 79,79( 1)°, γ = 75,00(1)°; structure refinement with 2662 independent reflections, R = 0.055) shows that the structure is polymeric and the O2PPh2 ligands function as double bridges between the tin atoms leading to the formation of centrosymmetric Sn2O4P2 eight-membered rings. The ethyl groups are in trans-position in the resulting octahedral environment around tin. The I. R. and Raman spectra of Et2Sn(O2PR2)2 (R = Ph, Me) have been discussed and assigned. The mass spectra of Et2Sn(O2PR2)2 show Sn(O2PR2)+ as the base peak.


2007 ◽  
Vol 72 (12) ◽  
pp. 1295-1308 ◽  
Author(s):  
G. Vuckovic ◽  
S.B. Tanaskovic ◽  
Z.M. Miodragovic ◽  
V. Stanic

Three new binuclear Co(II) mixed-ligand complexes with N,N?,N??,N???-tetrakis( 2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane (tpmc) and mono- or dicarboxylate ligands were prepared and some of their physical properties were determined. The general formulas: [Co2(HCOO)2tpmc](ClO4)2?4H2O, [Co2(CH3COO)2tpmc](ClO4)2 and [Co2(tpht)tpmc](ClO4)2?4H2O (tphtH2 = terephthalic acid) were proposed on the basis of elemental analyses (C,H,N) and molar conductivity. UV/Vis absorption and IR spectra, magnetic and CV measurements were used to study their geometries and properties. For the monocarboxylate complexes, an exo coordination of Co(II) with four nitrogens from tpmc and bis-bidentate bonded HCOO-/CH3COO- in the trans position is assumed. Tpmc adopts the chair conformation. For the dicarboxylate complex, it is supposed that a terephthalate dianion, as well as methylene chains from cyclam bridge two Co(II) atoms, while tpmc is in the boat conformation. The complexes were stable against chemical and electrochemical oxidation of Co(II) to Co(III). The data are compared with those for the previously published Cu(II) complexes containing the corresponding ligands and mutual similarities or differences were considered. Finally, some antibacterial activity of the complexes was found.


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