[M(L)2(NCS)2] Complexes (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); L = Hydrazide of Diphenylphosphinylacetic Acid)

Dithiocyanates of bis(hydrazidediphenylphosphinylacetic acid) M(II), where M is Mn, Fe, Co, Ni, Cu, and Zn were synthesized. Their magnetic properties were studied. All compounds were paramagnetic monomers with pseudooctahedral stereochemistry, except for the Zn(II) complex.     

Syntheses, structures, and properties of trinuclear complexes [M(bpca)(2)(M'(hfac)(2))(2)], constructed with the complexed bridging ligand [M(bpca)(2)] [M, M' = Ni(II), Mn(II); Cu(II), Mn(II); Fe(II), Mn(II); Ni(II), Fe(II); and Fe(II), Fe(II); Hbpca = Bis(2-pyridylcarbonyl)amine, Hhfac = Hexafluoroacetylacetone

Five trinuclear complexes [M(bpca)(2)(M'(hfac)(2))(2)] (where MM'(2) = NiMn(2), CuMn(2), FeMn(2), NiFe(2), and FeFe(2); Hbpca = bis(2-pyridylcarbonyl)amine; and Hhfac = hexafluoroacetylacetone) were synthesized almost quantitatively by the reaction of [M(bpca)(2)] and [M'(hfac)(2)] in 1:2 molar ratio, and their structures and magnetic properties were investigated. Three complexes, with M' = Mn, crystallize in the same space group, Pna2(1), whereas two complexes, with M' = Fe, crystallize in P4(1), and complexes within each set are isostructural to one another. In all complexes, [M(bpca)(2)] acts as a bis-bidentate bridging ligand to form a linear trinuclear complex in which three metal ions are arranged in the manner M'-M-M'. The central metal ion is in a strong ligand field created by the N(6) donor set, and hence the Fe(II) in the [Fe(bpca)(2)] moiety is in a low-spin state. The terminal metal ions (M') are surrounded by O(6) donor sets with a moderate ligand field, which leads to the high-spin configuration of Fe(II). Three metal ions in all complexes are almost collinear, and metal-metal distances are ca. 5.5 A. The magnetic behavior of NiMn(2) and NiFe(2) shows a weak ferromagnetic interaction between the central Ni(II) ion and the terminal Mn(II) or Fe(II) ions. In these complexes, sigma-spin orbitals of the central Ni(II) ion and those of terminal metal ions have different symmetry about a 2-fold rotation axis through the Ni-N(amide)-M'(terminal) atoms, and this results in orthogonality between the neighboring sigma-spin orbitals and thus ferromagnetic interactions.     

Magnetic properties and molecular structures of binuclear (2-pyrazinecarboxylate)-bridged complexes containing Re(IV) and M(II) (M = Co, Ni)

Three novel Re(iv) compounds, the mononuclear complex Bu(4)N[ReBr(5)(Hpyzc)] (1) and the heterobimetallic complexes [ReBr(5)(mu-pyzc)M(dmphen)(2)].2CH(3)CN [M = Co (2), Ni (3)] (Hpyzc = 2-pyrazinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. The structure of 1 consists of [ReBr(5)(Hpyzc)](-) complex anions and tetrabutylammonium cations, Bu(4)N(+). The Re(iv) is surrounded by five bromide anions and a N-donor Hpyzc monodentate ligand, in a distorted octahedral environment. The structures of 2 and 3 consist of dinuclear units [ReBr(5)(mu-pyzc)M(dmphen)(2)], with the metal ions linked by a pyzc bridge ligand, being bidentate toward M(II) and monodentate toward Re(IV). The environment of Re(IV) is the same as in 1, whereas M(II) is six-coordinate, being surrounded by four nitrogen atoms of two bidentate dmphen ligands and one oxygen atom and one nitrogen atom of the pyzc anion. The magnetic properties of 1-3 were investigated in the temperature range 2.0-300 K. 1 shows the expected magnetic behavior for a mononuclear Re(IV) complex with a weak intermolecular antiferromagnetic coupling at low temperatures. The bimetallic complexes exhibit an intramolecular ferromagnetic coupling between Re(IV) and the M(II) ion (Co, Ni).     

Single crystal circular and linear dichroism spectra and absolute configuration of M(en)3(NO3)2 (M = Zn(II), Cu(II), Ni(II), Co(II), Mn(II) and Ru(II)

The isomorphous single crystals of M(ethylenediamine)₃(NO₃)₂, where M is Zn(II), Ni(II) and Co(II), exhibit macroscopic optical activity as predicted by their acentric space group. Axial circular dichroism measurements on these pure crystals show conclusively that spontaneous resolution has occurred. The axial circular dichroism and orthoaxial linear dichroism spectra of these pure crystals, and of Cu(II), Ni(II), Co(II), Mn(II) and Ru(II) doped into the Zn(en)₃(NO₃)₂ crystal have been measured at ambient and cryogenic temperatures in the range from 7 to 35 kK. The first NO₃^? transition at 32.5 kK is assigned as ¹A ← ¹A based on its linear polarization and sign of rotational strength. The d-d transitions are assigned in the context of D₃ symmetry and reveal a small negative crystal field parameter k, consistent with theoretical prediction. A positive R for all d-d transitions is found to be associated with the Λ configuration for all of the complex ions, by correlation with the crystal and solution circular dichroism of Ru(en)₃²⁺.     

Ferro- and antiferromagnetic interactions in face-sharing trioctahedral Ni(II)Mn(II)Ni(II) and Ni(II)Fe(III)Ni(II) complexes with the same 1-5/2-1 spin system

Two heterotrinuclear complexes, [Mn(II)(Ni(II)L)2].2CH3OH (where H3L = 1,1,1-tris(N-salicylideneaminomethyl)ethane) and [Fe(III)(Ni(II)L)2]NO3.C2H5OH, consisting of three face-sharing octahedra have been prepared; although these complexes have closely related structures and have the same 1-5/2-1 spin system, they show completely different magnetic interactions between the adjacent metal ions: ferromagnetic (Ni(II)-Mn(II)) and antiferromagnetic (Ni(II)-Fe(III)).     

Cyano-bridged hexanuclear Fe4M2 (M = Ni, Co, Mn) clusters: spin-canted antiferromagnetic ordering of Fe4Ni2 cluster

Heterobimetallic hexanuclear cyano-bridged complexes, [{Fe(Tp)(CN)3}4{M(MeCN)(H2O)2}(2)].10H2O.2MeCN [M = Ni (1), Co (2), Mn (3); Tp = hydrotris(1-pyrazolyl)borate], have been synthesized in H2O-MeCN solution. Complexes 1-3 are isostructural and hexanuclear with [{Fe(Tp)(CN)3}4{M(MeCN)(H2O)2}2] units linked by hydrogen bonds to form a 2D-structure in the solid state. Complex 1 is a canted antiferromagnet that undergoes a field-induced spin-flop-like transition at approximately 1 T and 2 K. At 4.45 K 1 has a transition to paramagnetic state of noninteracting S = 4 magnetic clusters. However, 2 and 3 show antiferromagnetic intracluster coupling. Facile loss of solvent from 2 alters the local symmetry resulting in changing the intracluster interaction from antiferro- to ferromagnetic.     

Inorganic-organic framework structures; M(II) ethylenediphosphonates (M = Co, Ni, Mn) and a Mn(II) ethylenediphosphonato-phenanthroline

The reaction of nickel, cobalt, and manganese with 1,2-ethylenediphosphonic acid or 1,2-ethylenediphosphonic acid and 1,10-phenanthroline under hydrothermal conditions resulted in the pillared layered structures Co2(H2O)2(O3PC2H4PO3) (I) and Ni2(H2O)2(O3PC2H4PO3) (II), which are isostructural to a zinc phase that has previously been characterized by X-ray powder methods. In addition, a 1D chain structure, Mn(HO3P(CH2)2PO3H)(H2O)2(C12H8N2) (III), and a pillared layered structure, Mn(HO3P(CH2)2PO3H) (IV), were obtained. The structures of these phases were solved by single-crystal X-ray diffraction methods. The crystallographic data are as follows: compound I P21/n (No. 14), a = 5.6500(11) A, b = 4.7800(10) A, c = 15.330(3) A, beta = 98.50(3) degrees, V = 409.47(14) A3, Z = 2; compound II P21/n (No. 14), a = 5.5807(11) A, b = 4.7205(9) A, c = 15.250(3) A, beta = 98.55(3) degrees, V = 397.28(13) A3, Z = 2; compound III C2/c (No. 15), a = 12.109(2) A, b = 15.328(3) A, c = 9.848(2) A, beta = 108.88(3) degrees, V = 1729.5(6) A3, Z = 4; compound IV P (No. 2), a = 5.498(5) A, b = 7.715(6) A, c = 8.093(7) A, alpha = 82.986(12) degrees, beta = 75.565(12) degrees, gamma = 80.582(12)degrees, V = 326.7(5) A3, Z = 2. Magnetic measurements show antiferromagnetic behavior below TN = 7 K for I and 13 K for II.     

Ferromagnetic vs. antiferromagnetic coupling in bis(mu2-1,1-azido)dinickel(II) complexes with syn- and anti-conformations of the end-on azide bridges

Reaction of a 1 : 1 : 1 molar ratio of NiCl(2), NaN(3) and H(2)L, a tetradentate ligand N-(2-pyridyl)methyl)-N,N-bis(2'-hydroxy-3',5'-dimethylbenzyl)amine in methanol in presence of Et(3)N results in a turquoise precipitate, which affords deep green crystals of [Ni(2)(HL)(2)(N(3))(2)]*1.5CH(2)Cl(2) (1) and [Ni(2)(HL)(2)(N(3))(2)]*H(2)O (2) upon crystallization from CH(2)Cl(2)-MeOH or THF-MeOH, respectively. Both complexes reveal distorted octahedral NiN(4)O(2) coordination environments around the Ni(ii) centers with bis(micro-1,1-azido) bridging ligands. Complex 1 displays an unprecedented small Ni-N-Ni bridge angle of 90.4 degrees , whereas 2 contains the said angle of av. 98.7 degrees lying in the usual range observed for other comparable structures. The variable-temperature magnetic susceptibility together with the variable-field, variable-temperature (VTVH) magnetization measurements discern different ground states of S(t) = 0 for 1 and S(t) = 2 for 2. The magnetic behaviours of these compounds are discussed in the context of the known bis(end-on azido) bridging dinickel(II) complexes.     

Magneto-structural studies on heterobimetallic malonate-bridged M(II)Re(IV) complexes (M = Mn, Co, Ni and Cu)

The mononuclear Re(IV) compound of formula (PPh(4))(2)[ReBr(4)(mal)] (1) was used as a ligand to obtain the heterobimetallic species [ReBr(4)(μ-mal)Co(dmphen)(2)]· MeCN (2), [ReBr(4)(μ-mal)Ni(dmphen)(2)] (3), [ReBr(4)(μ-mal)Mn(dmphen)(2)] (4a), [ReBr(4)(μ-mal)Mn(dmphen)(H(2)O)(2)]·dmphen·MeCN·H(2)O (4b), [ReBr(4)(μ-mal)Cu(phen)(2)]·1/4H(2)O (5) and [ReBr(4)(μ-mal)Cu(bipy)(2)] (6) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline, phen = 1,10-phenanthroline and bipy = 2,2'-bipyridine). The structures of 2 and 5 (single-crystal X-ray diffraction) are made up of neutral [ReBr(4)(μ-mal)M(AA)] dinuclear units [AA = dmphen with M = Co (2) and AA = phen with M = Cu (5)] where the metal ions are connected through a malonate ligand which exhibits simultaneously the bidentate [at the Re(IV)] and monodentate [at the M(II)] coordination modes. The carboxylate-malonate group in them adopts the anti-syn conformation with intramolecular ReM separation of 5.098(8) (2) and 4.947(2) ? (5). The magnetic properties of 1-6 were investigated in the temperature range 1.9-295 K. The magnetic behaviour of 1 is the expected for a magnetically isolated Re(IV) complex with a large value of the zero-field splitting (2D ca. -70 cm(-1)) whereas weak antiferromagnetic interactions between Re(IV) and M(II) are observed in the heterobimetallic compounds 2 (J = -0.63 cm(-1)), 3 (J = -1.37 cm(-1)), 4a (J = -1.29 cm(-1)), 5 (J = -1.83 cm(-1)) and 6 (J = -0.26 cm(-1)). Remarkably, 4b behaves as a ferrimagnetic chain with regular alternating Re(IV) and Mn(II) cations (J = -2.64 cm(-1)).     

Clathrate formation in the [M(4-MePy)2 (NCS)2]-4-MePy systems,where M=Co(II), Ni(II), Zn(II), Cd(II); 4-MePy=4-methylpyridine

A number of complexes [M(4-MePy)_n (NCS)₂], where M=Co(II), Ni(II), Zn(II), Cd(II); n=2 or 4 have been synthesized and phase diagrams [M(4-MePy)₂(NCS)₂]-4-MePy have been studied. The forming compounds have been obtained and described with the help of IR-spectroscopy and thermal analysis. The structure of a molecular type with variable section channels, filled by two types guest-molecules (by a water molecule in the narrow part of the channel and by two 4-methylpyridine molecules in the broad part of the channel, with a total ratio guest: host being 1:1) for [Cd(4-MePy)₄ (NCS)₂]·0.67(4-MePy)·0.33H₂O has been defined by X-ray method. This clathrate is isostructural (X-ray powder diffractogram) to the anhydrous compound [Cd(4-MePy)₄ (NCS)₂]·0.67(4-MePy).     

Chiral molecular magnets: synthesis, structure, and magnetic behavior of the series [M(L-tart)] (M = Mn(II), Fe(II), Co(II), Ni(II); L-tart = (2R,3R)-(+)-tartrate)

A new series of layered magnets with the formula [M(L-tartrate)] (M = Mn(II), Co(II), Fe(II), Ni(II); L-tartrate = (2R,3R)-(+)-tartrate) has been prepared. All of these compounds are isostructural and crystallize in the chiral orthorhombic space group I222, as found by X-ray structure analysis. Their structure consists of a three-dimensional polymeric network in which each metal shows distorted octahedral coordination bound to four L-tartrate ligands, two of which chelate through an alcohol and a carboxylate group and the other two bind terminally through a monodentate carboxylate group. The chirality of the ligand imposes a Delta conformation on all metal centers. Magnetically, the paramagnetic metal centers form pseudotetragonal layers in which each metal is surrounded by four other metals, with syn,anti carboxylate bridges. These salts show intralayer antiferromagnetic or ferromagnetic interactions, depending on the electronic configuration of the metal, and weak interlayer antiferromagnetic interaction. In all cases the magnetic properties are strongly affected by the anisotropy of the system, and the presence of magnetic canting has been found. The Mn derivative behaves as a weak ferromagnet with a critical temperature of 3.3 K. The Ni derivative shows very unusual magnetic behavior in that it exhibits antiferromagnetic ordering below 6 K, the onset of spontaneous magnetization arising from spin reorientation into a canted phase below 4.5 K, and a field-induced ferromagnetic state above 0.3 T at 2 K, behavior typical of metamagnets. The Fe and Co derivatives show antiferromagnetic interactions between spin carriers, but do not order above 2 K.     

Weak M(II)-azide-4,4'-bipy ferromagnets based on unusual diamondoid (M = Mn) and 2D arrays (M = Co, Ni)

Four compounds of general formula [M(4,4'bipy)(N(3))2](n) (M = Mn (1), Zn (2), Co (3), Ni (4)) have been synthesized and magnetostructurally characterized by means of X-ray diffraction analysis, IR and ESR spectroscopies, and measurements of the magnetic susceptibility and magnetization. Compound 1 (C(10)H(8)N(8)Mn) crystallizes in the tetragonal P4(3)2(1)2 space group, Z = 4, with a = 8.229(2), b = 8.229(2), and c = 16.915(2) A. It exhibits an acentric 3D structure where Mn(II) ions are linked through EE-azide groups resulting in a diamondoid network. The 4,4'bipy ligands are coordinated on the axial positions of the octahedral spheres reinforcing the intermetallic connections. Weak ferromagnetism arising from spin canting is observed for compound 1. Compounds 2, 3, and 4 are proposed to be isomorphous and would consist of a 2D array where alternating EO + EE/EO + EE/EO + EO azide-chains are linked by 4,4'bipy ligands resulting in pi-pi stacked pyridyl-columns. The azido ligand dispositions in compounds 3 and 4 make possible systems of type -AF-AF-F-, which would give rise to a topological ferromagnetic behavior.     

Ni(cyclam)(mu(1,3)-dca)2Cu(mu(1,5)-dca)2]: a genuine 3D bimetallic coordination polymer containing both mu(1,3)- and mu(1,5)-bidentate dicyanamide bridges and a ferromagnetic interaction between copper(II) and nickel(II) ions

The structure of [Ni(cyclam)(mu(1,3)-dca)2Cu(mu(1,5)-dca)2], a genuine 3D dicyanamide-bridged bimetallic coordination polymer, is made up of 2D [Cu(mu(1,5)-dca)2]n layers connected by [Ni(cyclam)(mu(1,3)-dca)2] bridging moieties; it exhibits a ferromagnetic exchange interaction between copper(II) and nickel(II) ions through the mu(1,3)-bidentate dicyanamide bridges.     

Magnetic Properties of M3[Fe(Cn)6]2Xh2O (M = Co (II), Ni(II), Cu(II), Zn(II))

Compounds of the type M₃[Fe(CN)₆]₂XH₂O (M = Co(II), Ni(II), Cu(II), and Zn(II)) were prepared and magnetic properties of their powders were investigated by means of EPR spectra, Mössbauer effect and magnetic susceptibility measurements. The temperature dependence of the magnetization for the complexes Co₃[Fe(CN)₅]₂- 10H₂O, Ni₃[Fe(CN)₆]₂-10H₂O and Cu₃[Fe(CN)₆]₂-4H₂O revealed that below the critical temperatures 15, 22 and 20 K respectively, these complexes have zero-field magnetization. The magnetic hysteresis at 10 K for Co(II), Ni(II) and Cu(II) complexes was observed. Mössbauer spectra at 4.2 K for the compounds are discussed.     

Transition metal containing decatungstosilicate dimer [M(H(2)O)(2)(gamma-SiW(10)O(35))(2)](10-) (M = Mn(2+), Co(2+), Ni(2+))

The new, monometal substituted silicotungstates [Mn(H(2)O)(2)(gamma-SiW(10)O(35))(2)](10-) (1), [Co(H(2)O)(2)(gamma-SiW(10)O(35))(2)](10-) (2) and [Ni(H(2)O)(2)(gamma-SiW(10)O(35))(2)](10-) (3) have been synthesized and isolated as the potassium salts K(10)[Mn(H(2)O)(2)(gamma-SiW(10)O(35))(2)] x 8.25 H(2)O (K-1), K(10)[Co(H(2)O0(2)(gamma-SiW(10)O(35))(2)] x 8.25 H(2)O (K-2) and K(10)[Ni(H(2)O)(2)(gamma-SiW(10)O(35))(2)] x 13.5 H(2)O (K-3), which have been characterized by IR spectroscopy, single crystal X-ray diffraction, elemental analysis and cyclic voltammetry. Polyanions 1-3 are composed of two (gamma-SiW(10)O(36)) units fused on one side via two W-O-W' bridges and on the other side by an octahedrally coordinated trans-MO(4)(OH(2))(2) transition metal fragment, resulting in a structure with C(2v) point group symmetry. Anions 1-3 were synthesized by reaction of the dilacunary precursor [gamma-SiW(10)O(36)](8-) with Mn(2+), Co(2+) and Ni(2+) ions, respectively, in 1 M KCl solution at pH 4.5. The electrochemical properties of 1-3 were studied by cyclic voltammetry and controlled potential coulometry in a pH 5 buffer medium. The waves associated with the W-centers are compared with each other and with those of the parent lacunary precursor [gamma-SiW(10)O(36)](8-) in the same medium. They appear to be dominated by the acid-base properties of the intermediate reduced species. A facile merging of the waves for 3 is observed while those for 1 and 2 remain split. Controlled potential coulometry of the single wave of 3 or the combined waves of 1 and 2 is accompanied by catalysis of the hydrogen evolution reaction. No redox activity was detected for the Ni(2+) center in 3, whereas the Co(2+) center in 2 shows a one-electron redox process. The two-electron, chemically reversible process of the Mn(2+) center in 1 is accompanied by a film deposition on the electrode surface.     

Synthesis, structure, and magnetism of heterometallic carboxylate complexes [MnIII2M(II)4O2(PhCOO)10(DMF)4], M = Mn(II), Co(II), Ni(II)

Three new homo- and heterometallic hexanuclear complexes [Mn(2)M(II)(4)O(2)(PhCOO)(10)(DMF)(4)] (with M = Mn (1), Co (2) or Ni (3) and DMF = dimethylformamide) have been synthesized by redox generation of benzoate ligands from benzaldehyde in a one-pot reaction. All of the compounds are isostructural and crystallize in the I-42d space group of the tetragonal system, data for 1: a = 27.2249(8) Angstroms, c = 25.5182(5) Angstroms, R1 = 0.0681. The crystal structure contains isolated molecules. Each molecule consists of 2 x Mn(III) surrounded by four M(II) ions to form two edge-sharing OMn(2)M(2) tetrahedra giving rise to the [Mn(2)M(4)O(2)] core. The coordination sphere of each metal is completed by the bridging benzoate ligands and DMF molecules. The magnetic susceptibilities of 1-3 have been measured in the 1.8 K < T < 300 K temperature range. The magnetic susceptibilities for 1 and 2 pass through a broad maximum at low temperature which is characteristic of the diamagnetic ground state, while for 3 no maximum is detected down to 1.8 K. The magnetic data have been interpreted quantitatively for 1 and 3 on the basis of spin exchange interactions between the metallic centers (spin Hamiltonian for a pair being H(AB) = -J(AB) S(A).S(B)). Single-crystal measurements on [Mn(6)O(2)(PhCOO)(10)(CH(3)CN)(4)] (4) show that significant magnetic anisotropy develops at low temperature.     

Structure of Mn(II), Co(II), Ni(II), and Cu(II) complexes with triformylmethane

Previously unknown [ML₂(H₂O) _n ] bischelates, where M is Mn(II), Co(II), Ni(II), or Cu(II) and L is deprotonated triformylmethane, are studied by X-ray diffraction analysis. It is revealed that in the crystals of all compounds there are multiple hydrogen bonds linking bischelate molecules into polymer layers or a single framework. The character of the temperature dependence of the effective magnetic moment [ML₂(H₂O) _n ] indicates the existences of weak intracrystalline exchange interactions between the unpaired electrons of the paramagnetic centers.     

Synthesis and characterization of (smif)2M(n) (n = 0, M = V, Cr, Mn, Fe, Co, Ni, Ru; n = +1, M = Cr, Mn, Co, Rh, Ir; smif =1,3-di-(2-pyridyl)-2-azaallyl)

A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe(3))(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX(2) variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl(3)(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl(3)(THF)(3) in the presence of NaBPh(4) gave [(smif)(2)Ir]BPh(4) (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh(2)(O(2)CCF(3))(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC(nb) (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (ε ≈ 10,000-60,000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr.     

[MPy4(NCO)2]-2Py clathrates (M = M(II) = Mn,Fe, Co,Ni, Cu,Zn, Cd; Py = pyridine)

The title compounds form an iso structural series and are isomorphic with other [MPy₄X₂]-2Py clathrates (XRD, KM4 diffractometer, cell parameters and space group Ccca from 17–80 reflections). In the clathrate [NiPy₄(NCO)₂]-2Py studied in detail (XRD, CAD-4 diffractom eter, λCuK_α, Ω/2θ scan mode, θ_max = 78‡, 990 strong reflections, 104 parameters, R = 0.053), the host molecule has 222 symmetry, and the twofold axes run along the coordination bonds. The transoctahedral environment of nickel consists of six nitrogen atoms of four pyridine and two isocyanate ligands. The coordination polyhedron is slightly distorted due to changes in the bond lengths. The molecule has a propeller conformation. The guest molecules lie in the cavities of the crystal structure in conformity with the van der Waals type of packing. The host complex [NiPy₄(NCO)₂] (XRD, CAD-4 diffractometer, 4615 strong reflections, 560 parameters, R-0.037) crystallizes in the triclinic crystal system (space group P1) with two independent asymmetric molecules in the unit cell. The molecular structure is analogous to that in the ciathrate phase, but the coordination angles are severely distorted; one of the molecules acquires a distorted propeller conformation, and the other, a centrosvmmetric conformation, which is less favorable. While being structurally identical, the [MPy₄(NCO)₂]-2Py clathrates differ heavily in the properties. The first four complexes dissociate to host complexes, and their thermal stability changes in the sequence Mn< Fe< Co< Ni; the Cu and Zn clathrates decompose in one step to dipyridine complexes with decomposition of host complexes. Decomposition of the Cd ciathrate follows one of these patterns depending on conditions. The results are compared with those for other known systems. Synthetic procedures are given. Translated fromZhurnal Strukturnoi Khimii, Vol. 40, No. 5, pp. 935–953, September–October, 1999.