Sigurd Hoehne

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen XX. Darstellung, eigenschaften und kristallstruktur von λ4-thia-λ5-phospha-h2-metallabicyclo[2.2.1]heptadienen und ihre verwendung zur synthese von metallorganischen und organischen verbindungen

Abstract The novel λ 4 -thia-λ 5 -phospha- h 2 -manganabicyclo[2.2.1]heptadienes (OC) 3 Mn[ CR 2 CR 2 CR 2 CR 2 PR 1 2 S ] (R 1 = CH 3 , C 6 H 5 ; R 2 = CO 2 CH 3 , CO 2 C 2 H 5 , CO 2 C 6 H 11 ) are formed by action of the activated alkynes R 2 C  CR 2 on the heterocycles [(OC) 4 MnPR 1 2 S] 2 via the isolable, five-membered heterometallacyclopentadienes (OC) 4 MnSPR 1 2 C(R 2 )C (R 2 ). The compound with R 1 = CH 3 and R 2 = CO 2 CH 3 crystallizes in the triclinic space group P 1 with Z = 2 and separates quantitatively the thiophene derivative CR 2 CR 2 CR 2 CR 2 S under CO pressure or by reaction with (NH 4 ) 2 Ce(NO 3 ) 6 . The use of various acetylenes and of acetylenes with different alkyl groups yields the unsymmetric substituted manganabicycloheptadienes (OC) 3 Mn[ CR 4 CR 3 CR 2 CR 2 P(CH 3 ) 2 S ] (R 2 = CO 2 CH 3 , R 3 = R 4 = CO 2 C 2 H 5 ; R 2 = R 4 = CO 2 CH 3 , R 3 = H). With propionic acid methylester the alkyne insertion proceeds regiospecifically. With Raney nickel selective S elimination under ring contraction and formation of the λ 4 -phospha- h 2 -manganabicyclo[2.1.1]hexenes (OC) 3 Mn[ CR 2 CR 3 CR 2 CR 2 P R 1 2 ] (R 1 = CH 3 : R 2 = R 3 = CO 2 CH 3 , CO 2 C 2 H 5 ; R 2 = CO 2 CH 3 , R 3 = H; R 1 = C 6 H 5 : R 2 = R 3 = CO 2 C 2 H 5 ) occurs. (OC) 3 Mn[ CR 2 CR 3 CR 2 CR 2 P (CH 3 ) 2 ] (R 2 = R 3 = CO 2 CH 3 ) crystallizes in the monoclinic space group P 2 1 / m with Z = 2. The IR and NMR spectra of the heterocycles are discussed in detail.

Das verhalten von mono- und diorganylphosphinsulfiden gegenüber metallcarbonylsystemen ☆: XVIII. Die kristall- und molekülstrutur von 3,3,3,3,6,6,6,6-oktacarbonyl-2,2,5,5-tetraphenyl-1,4-dioxa-2,5-diphospha-3,6-dimanganacyclohexan, [-(OC),MnP(C6H5)2O-]2

Abstract The inorganic six membered heterocycle [-(OC) 4 MnP(C 6 H 5 ) 2 O-] 2 is formed by elimination of HBr in the presence of NH 3 from (OC) 4 BrMnP(C 6 H 5 ) 2 OH. It crystallizes in the monoclinic space group P 2 1 / c with four molecules in the unit cell and has a twisted boat conformation.

Chemie polyfunktioneller liganden: LXXIII. Synthese, struktur und reaktionsverhalten von cryptanden (bzw. spheranden) mit den heteroelementen arsen, sauerstoff, schwefel und stickstoff

Abstract The reaction of N(CH 2 CH 2 Cl) 3 (I) with KAs(C 6 H 5 ) 2 ·dioxane ( 1 2 ) in THF yields, as Sacconi et al. reported earlier, 80% of N[CH 2 CH 2 As(C 6 H 5 ) 2 ] 3 (II). II is now obtained in a still higher quantity from the reaction of [HN(CH 2 CH 2 Cl) 3 ]Cl (III) with NaAs(C 6 H 5 ) 2 in liquid ammonia. Treatment of II with gaseous HI in dry CH 2 Cl 2 results in the formation of [HN(CH 2 CH 2 AsI 2 ) 3 ]I (IV), which is isolated by recrystallisation from THF as [HN(CH 2 CH 2 AsI 2 ) 3 ]I · THF ( 1 1 ) (IVa). IVa reacts with H 2 O/NH 3 or H 2 S/N(C 2 H 5 ) 3 to give the novel cryptands [N(CH 2 CH 2 ) 3 ] 8 -(As 4 O 4 ) 6 (V) or [N(CH 2 CH 2 ) 3 ] 8 (As 4 S 4 ) 6 (VI), which also can be denoted as spherands. The reaction of V with dry gaseous HCl in benzene leads to [HN(CH 2 -CH 2 AsCl 2 ) 3 ]Cl (VII). All the new compounds are characterized, as far as possible, by their IR, FIR, Raman, 1 H NMR and mass spectra. To determine the structure of V a single X-ray crystal study was carried out. Moreover II, which is already well-known but not completely characterized, is included in this discussion only for spectroscopic comparison.

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen XXXV. Metallzentrierte C-C-verknüpfung durch reduktive dimerisierung von thioaroyl-gruppen;synthese, abfangreaktionen und kristallstrukturen von dithiolen-komplexen

Abstract The E- and Z-isomeric dithiolene complexes [(OC)5MnS]2(μ-CR1CR1) (R1 = C6H4X-4; X = H, F, Cl, CH3) are formed by the manganese-induced reductive dimerization of the thioaroyl chlorides SC(R1)Cl via a carbenoid intermediate which is not isolable. The Z-isomers stabilize by coordination of the free electron pairs of the sulphur on the manganese atoms under CO elimination, to give the cis-dithiolene compounds R12[η2-C(μ2-S)C(μ2-S)]Mn2(CO)6. E-[(OC)5MnS]2(μ-CR1CR1), (R1 = C6H4F-4) and (C6H5)2[η2-C(μ2-S)C(μ2-S)]Mn2(CO)6 crystallize in the monoclinic space group P21/n and P21/a with Z = 2 and 4, respectively. The E-dithiolene compounds react with activated alkynes R2CCR2 (R2 = CO2C6H11, CO2CH(CH3)2, CO2C2H5) to form the trapping products E-[ CR 2 CR 2 -(OC) 4 MnS ]2(μ-CR1CR1), containing two thiamanganacyclobutene rings connected by a centre of symmetry. For R2 = C6H4F-4 the compound crystallizes in the triclinic space group P 1 with Z = 1.

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen : XVIII. Irreversible ringkontraktion eines manganacyclohexans zu einem manganacyclopentan

Abstract The six-membered manganacyclohexane (OC)4MnPPh2CH2CH2CH2CH2 is contracted into the cyclopentane derivative (OC)4MnPPh2CH2CH2CHCH3 when it is heated in n-hexane at 100°C in a sealed tube. The heterocycles crystalize orthorhombic and monoclinic in the space groups P212121 and P21/c respectively, with Z  4.

Synthesis and X-ray crystal structure of a macrocyclic arsa-aza-oxa-cryptand containing eight-membered As4O4 rings

Reaction of N[(CH2)2As(C6H5)2]3(1) with gaseous HI leads to{HN[(CH2)2Asl2]3}I2(2) and hydrolysis of (2) with H2O–NH3 in tetrahydrofuran gives [N(CH2CH2)3]8(As4O4)6(3); single crystal X-ray diffraction shows that one moleculer of (3) contains six eight-membereds As4O4ring connected together by triethylamine units.

Präparative, spektroskopische und kristallographische Untersuchungen an Phosphinato-Komplexen des Rheniums mit verschiedenen einzähnigen Liganden /Preparative, Spectroscopic and Crystallographic Investigations on Phosphinato Complexes of Rhenium with Various Unidentate Ligands

Abstract The stable phosphinato complexes [μ-R2PO2Re(CO)3L]n (1, 2b-f) [L = THF (a), py (b), NH3 (c), P(C6H5)3 (d), As(C6H5)3 (e), P(C6H11)3 (f), O(C2H5)2 (g)] are obtained by addition of the ligands L to the compounds [μ-R2PO2Re(CO)3]n (1, 2) [R = CH3 (1), C6H5 (2)] at 20-40 °C (1, 2c: -35 °C). 1, 2b, d, e are also formed when THF in 1, 2a is substituted by the ligands b, d, and e. The unstable ether adducts 1, 2 g which result photochemically from Re2(CO)10 and the acids R2PO2H, are transformed to 1, 2 by elimination of ether. At 20 °C 1, 2 a react with liquid ammonia to give the ionic complexes [(OC)3Re(NH3)3][O2PR2] (1, 2h). On the basis of their mass and vibrational spectra, and a crystallographic investigation, the methyl [1a-f] and phenyl compounds [2a-f] are dimeric and oligomeric, respectively. The rhenium atoms are bridged via R2PO2- ligands (phosphinato-O,O′). 1a crystallizes monoclinic in the space group C2/m with Z = 2.