ESR-Untersuchungen an μ-Dichloro-bis[chloro-bis(N,N-diäthyldiselenocarbamato)molybdän(V)]-dichlorid, [Mo2CI4(däsc)4]CI2

EPR-Investigations of α-Dichloro-bis[chloro?bis(N,N?diethyldiselenocarbamato)molybdänum(V)] dichloride, [Mo₂Cl₄(däsc)₄]Cl₂. Preparation and bonding properties of the coordination sphere of [Mo₂Cl₄(däsc)₄]Cl₂ studied by EPR, are reported. The EPR-spectrum at 77°K can be described by an axial symmetric spin-HAMILTONian, the parameters of which are g| = 2.046, g|= 1.996, A| = 53.5 · 10^?4 cm^?1, and A| = 22.8 · 10^?4 cm^?1. No ⁷⁷Se-ligand hyperfine structure could be observed. The very high g-values are explained as being caused by strong ligand spin-orbit interaction, CT-contributions and a high degree of co valency of tho Mo? Se bond. Using an MO-model of the symmetry C_4v, the bonding parameters of the first coordination sphere have been calculated.     

Acetylenbis(phosphonigsäurediamide), -bis(phosphonigsäurefluoridamide) und -bis(phosphonigsäuredifluorid)

Acetylene Bis(Phosphonous Diamides), Bis(Phosphonous Fluoride Amides), and Bis-(Phosphonous Difluoride) Synthesis and properties of the acetylene bis(phosphonous diamides) 2 – 5 , the acetylene bis(phosphonous fluoride amides) 6 and 7 and of acetylene bis(phosphonous difluoride), 8 , are described. The result of the X-ray structural analysis of 2 is reported.     

N-Phenylquecksilber-N,N-bis(phosphorsäurediphenylester)-imid

N-Phenylmercury-N,N-bis(phosphoric diphenylester)imide Synthesis, properties, and structure of the title compound are described.     

Mixed Ligand Complexes of Cobalt(II) – Synthesis,Structure, and Properties of Co4(thd)4(OEt)4

Synthesis, crystal structure, thermal stability, and magnetic properties of mixed‐ligand complexes of cobalt(II) with ß‐diketonato (thd = C₁₁H₁₉O₂^?) and alkoxides (OR mainly OMe = methoxide = CH₃O^? or OEt = ethoxide = C₂H₅O^?) are reported. Direct reaction between Co(thd)₂ ( 1 ) and EtOH gives a new complex with the structural formula [Co₄(thd)₄(OEt)₄] ( 2 ) whereas MeOH correspondingly reacts to [Co₄(thd)₄(OMe)₄(MeOH)₄] ( 3 ). The yield of these products decreases with increasing size of the R group owing to increased solubility of 1 in the alcohol. The structure of 2 is determined from single‐crystal X‐ray diffraction data. At 100 K 2 takes a monoclinic structure (space group C2/c): a = 15.108(2), b = 19.428(2), c = 21.240(3) Å, and β = 108.882(2)°. At 295 K 2 has transformed to a closely related orthorhombic structure (space group Fddd): a = 15.233(3), b = 19.712(3), c = 40.916(7) Å. Protracted hydrolysis accompanied by oxygenation of complexes 2 and 3 in laboratory air (viz. simultaneous exposure to moisture and oxygen) leads to a new complex 4 with empirical formula corresponding to [Co(thd)(OH)(O₂)]. Magnetic susceptibility data show that Co takes the valence state II in all complexes 1 – 4 . For 4 this implies that dioxygen has to form an adduct‐like association to the rest of the complex. Unfortunately complex 4 has hitherto only been obtained in the amorphous state, but all here produced evidences point at 4 as a distinct entity and that products of 4 obtained from 2 and 3 are chemically identical (but differ somewhat with regard to short‐ and longer‐range order in the atomic arrangement). The interatomic distances in the crystal structure of complexes 1 – 3 are briefly discussed in terms of the bond‐valence concept.     

Beiträge zur Chemie des Phosphors. 94. Tetraphenyl-cyclotetraphosphan, (PPh)4, und 1,2,3-Triphenyl-4-tert-butyl-cyclotetraphosphan, (PPh)3(PBut)

Contributions to the Chemistry of Phosphorus. 94. Tetraphenyl-cyclotetraphosphane, (PPh)₄, and 1,2,3-Triphenyl-4-tert-butyl-cyclotetraphosphane, (PPh)₃(PBu^t) The homocyclic four-membered phosphorus ring compounds tetraphenyl-cyclotetra-phosphane, (PPh)₄ ( 1 ), and l,2,3-triphenyl-4-tert-butyl-cyclotetraphosphane, (PPh)₃(PBu^t) ( 2 ), are obtained as main products by [3+l]-cyclocondensation of K(Ph)P? P(Ph)? P(Ph)K or Me₃Si(Ph)P? P(Ph)? P(Ph)SiMe₃ with PhPCl₂ or Bu^tPCl₂ respectively under suitable reaction conditions. At room temperature in solution 1 rearranges mostly to the oligomeric (PPh)₅, whereas 2 is remarkably stable. The ³¹P-NMR parameters of the mixed substituted four-membered ring compound 2 are reported and discussed.     

Drei Heterocubanartige (MII4O4)‐Typ Verbindungen (M = FeII,CoII, NiII)

By reaction of M^IICl₂·x H₂O (M = Fe (x = 4), Co, Ni (x = 6)) and LiOH·H₂O in diethylene glycol (DEG) rod‐like crystals of the composition M^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ are formed. According to X‐ray diffraction data obtained by both, single crystals and powders, the Co^II and Ni^II compounds crystallize monoclinic with C2/c (Co^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 1 ): a = 2084.1(4), b = 919.0(2), c = 1754.0(4) pm, β = 124.3(1)°, Z = 4; Ni^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 2 ): a = 2055.2(4), b = 932.1(2), c = 1727.4(4) pm, β = 125.2(1)°, Z = 4), whereas Fe^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 3 ) crystallizes tetragonal with (a = 1251.4(2), c = 915.3(2) pm, Z = 2). All compounds exhibit analogous molecular structures which are built of a heterocubane‐type core consisting of four metal ions and four deprotonated oxygen atoms of four coordinated diethylene glycol molecules. Neutrality of charge is realized by additional coordination of four chloride anions. In addition to the structural characterization, the thermal and magnetical properties of the title compounds are investigated in detail.     

Heterobimetallic Clusters of Copper(I) with Trithiotungstate and Trithiomolybdate. Synthesis and Characterization of the Octanuclear Clusters [Et(4)N](4)[M(4)Cu(4)S(12)O(4)] (M = Mo, W) and the Dodecanuclear Clusters [M(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (M = Mo, W; TMEN = N,N,N',N'-Tetramethylethylenediamine)

Synthetic methods for [Et(4)N](4)[W(4)Cu(4)S(12)O(4)] (1), [Et(4)N](4)[Mo(4)Cu(4)S(12)O(4)] (2), [W(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (3), and [Mo(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (4) are described. [Et(4)N](2)[MS(4)], [Et(4)N](2)[MS(2)O(2)], Cu(NO(3))(2).3H(2)O, and KBH(4) (or Et(4)NBH(4)) were used as starting materials for the synthesis of 1 and 2. Compounds 3 and 4 were produced by reaction of [Et(4)N](2)[WOS(3)], Cu(NO(3))(2).3H(2)O, and TMEN and by reaction of [Me(4)N](2)[MO(2)O(2)S(8)], Cu(NO(3))(2).3H(2)O, and TMEN, respectively. Crystal structures of compounds 1-4 were determined. Compounds 1 and 2 crystallized in the monoclinic space group C2/c with a = 14.264(5) ?, b = 32.833(8) ?, c = 14.480(3) ?, beta = 118.66(2) degrees, V = 5950.8(5) ?(3), and Z = 4 for 1 and a = 14.288(5) ?, b = 32.937(10) ?, c = 14.490(3) ?, beta = 118.75(2) degrees, V = 5978.4(7) ?(3), and Z = 4 for 2. Compounds 3 and 4 crystallized in the trigonal space group P3(2)21 with a = 13.836(6) ?, c = 29.81(1) ?, V = 4942(4) ?(3), and Z = 3 for 3 and a = 13.756(9) ?, c = 29.80(2) ?, V = 4885(6) ?(3), and Z = 3 for 4. The cluster cores have approximate C(2v) symmetry. The anions of 1 and 2 may be viewed as consisting of two butterfly-type [CuMOS(3)Cu] fragments bridged by two [MOS(3)](2-) groups. Eight metal atoms in the anions are arranged in an approximate square configuration, with a Cu(4)M(4)S(12) ring structure. Compounds 3 and 4 can be considered to consist of one [M(4)Cu(4)S(12)O(4)](4-) (the anions of 1 and 2) unit capped by Cu(TMEN)(+) groups on each M atom; the Cu(TMEN)(+) groups extend alternately up and down around the Cu(4)M(4) square. The electronic spectra of the compounds are dominated by the internal transitions of the [MOS(3)](2-) moiety. (95)Mo NMR spectral data are investigated and compared with those of other compounds.     

(OLi2Ca4)3[ReN4]4, ein Nitridorhenat(VI)‐Oxid

(OLi₂Ca₄)₃[ReN₄]₄, a Nitridorhenate(VI) Oxide Black single crystals of (OLi₂Ca₄)₃[ReN₄]₄ were prepared from the elements (molar ratio Li : Ca : Re = 6 : 1 : 1) by reaction with molecular nitrogen at 900 °C; oxygen content results from a leak in the gas supply. The nitridorhenate(VI)‐oxide is an isotype of (OLi₂Ca₄)₃[MN₄]₄ (M = Mo^VI, W^VI). These compounds are obtained under similar reaction conditions in the presence of small amounts of oxygen containing impurities (Li‐/Ca‐hydroxides). The crystal structure of (OLi₂Ca₄)₃[ReN₄]₄ was determined by single crystal methods (cubic; I43d (# 220); a = 1315.88(9) pm; Z = 4) and can be derived from the Th₃P₄ type structure by hierarchical replacements: Th ≙ (OLi₂Ca₄)⁸⁺‐tetragonal bipyramids and P ≙ [Re^VIN₄]^6–‐tetrahedra.     

1, 3, 4, 4'‐Tetra(triphenylphosphanimin)‐2‐iodo‐2‐butenal‐4‐carboniumiodid, [O=C(NPPh3)C(I)=C(NPPh3)‐C(NPPh3)2]+I‐

Pale yellow single crystals of [O=C(NPPh₃)C(I)=C(NPPh₃)‐C(NPPh₃)₂]⁺I^‐·1.5 thf ( 1 ·1.5 thf) have been obtained by the reaction of INPPh₃ with thallium in thf suspension. They are characterized by IR spectroscopy and by a crystal structure determination. 1 ·1.5 thf crystallizes in the monoclinic space group P2₁/n, Z = 4, lattice dimensions at ‐83?C: a = 1101.7(1), b = 3449.0(2), c = 2000.4(1) pm, β = 104.88(1)?, R₁ = 0.0382. 1 can be understood as a cationic variation of (Z)‐2‐butenale in which all H atoms are substituted by triphenylphosphoraneimine residues and by a iodine atom, respectively.     

(Z)-4,7-Octadiensäure-äthylester und (Z)-Buttersäure-3,5-hexadienylester,zwei neue Aromastoffe der roten Passionsfrucht

Ethyl (Z)-4,7-Octadienoate and (Z)-3,5-Hexadienyl Butyrate, two New Aroma Components of the Purple Passionfruit The isolation of ethyl (Z)-4,7-octadienoate ( 1 ) and (Z)-3,5-hexadienyl butyrate ( 2 ), two new and important aroma constituents of the purple passionfruit (Passiflora edulis SIMS ) is reported. Ester 1 was synthesized by two different routes: (1) via a Wittig reaction between the known 4-oxobutyrate 4 and 3-butenylidenephosphorane, and (2) by thermolysis of (Z)-8-acetoxy-4-octenoate 7 which was readily accessible from (Z,Z)-1,5-cyclooctadiene. Ester 2 was prepared from the known hex-3-yn-5-en-1-ol ( 8 ) by a stereoselective (Z)-reduction of the triple bond to 9 , using Rieke's active metallic zinc, followed by esterification. The organoleptic properties and the taste threshold values of 1 and 2 are given.