Heteronukleare Komplexverbindungen mit Metall—Metall-Bindungen. VIII. Neue heterodinukleare Komplexe mit Bindungen zwischen Kupfer(I) und Mangan(–I), Eisen(–I) oder Cobalt(–I)

Heteronuclear Coordination Compounds with Metal—Metal Bonds. VIII. New Heterodinuclear Complexes with Bonds between Copper(I) and Manganese(?I), Iron(?I), or Cobalt(?I) [(en)Cu? Mn(CO)₅] ( 1a ), [(dien)Cu? Mn(CO)₅] ( 1b ), [(en)Cu? Fe(CO)₃(NO)] ( 2a ), [(dien)Cu? Fe(CO)₃(NO)] ( 2b ), [(en)Cu? Co(CO)₄] ( 3a ), and [(dien)Cu? Co(CO)₄] ( 3b ) are new heterobinuclear metal—metal bonded complexes. The geometry of the [Mn(CO)₅]^?, [Fe(CO)₃(NO)]^?, and [Co(CO)₄]^? ions is distorted only to a less extend in accord with a heteropolar bond to copper.     

Synthesis and Structures of Dinuclear Copper(I) and Silver(I) 1, 3‐Bis[(2‐chloro)benzene]triazenide Complexes

In the presence of Et₃N, the reaction of 1, 3‐bis[(2‐chloro)benzene]triazene (HL) with CuCl or AgNO₃ gives the triazenide complexes {Cu₂(L)₂} ( 1 ) and {Ag₂(L)₂} ( 2 ), respectively. The X‐ray crystal structures of both complexes were obtained. The metal–metal distances (Cu ··· Cu and Ag ··· Ag) are 2.4974(5) and 2.7208(5) Å, respectively.     

Cobalt(II)-organische Phosphaniminato-Komplexe mit Heterocuban-Struktur. Kristallstrukturen von [CoBr(NPR3)]4 mit R = Me,Et, [Co(C≡C–CMe3)(NPMe3)]4 und [Co(C≡C–SiMe3)(NPEt3)]4

Organo-Cobalt(II) Phosphorane Iminato Complexes with Heterocubane Structures. Crystal Structures of [CoBr(NPR₃)]₄ with R = Me, Et, [Co(C≡C–CMe₃)(NPMe₃)]₄, and [Co(C≡C–SiMe₃)(NPEt₃)]₄ The phosphorane iminato complexes [CoBr(NPR₃)]₄, which are accessible by reaction of CoBr₂ with the silylated phosphorane imines Me₃SiNPR₃ (R = Me, Et) in the melt at 180 °C and in the presence of KF, can be transformed into the alkynyl complexes [Co(C≡C–CMe₃) · (NPMe₃)]₄ and [Co(C≡C–SiMe₃)(NPEt₃)]₄ on obtaining the heterocubane structures, when caused to react with the lithium organic reagents LiC≡C–CMe₃ and LiC≡C–SiMe₃ in THF at 0 °C. According to the crystal structure analyses all four of the compounds form heterocubane structures with only slightly distorted Co₄N₄ cubic structures.     

Enantioselektive Katalysen. 155 [1] (Cymol)Ruthenium‐Halbsandwich‐Komplexe mit Pyrroloxazolin‐Liganden — Synthese,Stereochemie, Katalyse

Asymmetric Catalysis. 155 [1] (Cymene)Ruthenium Halfsandwich Complexes with Pyrroleoxazoline Ligands — Synthesis, Stereochemistry, Catalysis The (cymene)ruthenium halfsandwich complexes K1 and K2 with chiral pyrroleoxazoline ligands were synthesized and characterized. The complexes form diastereomers, which only differ in the metal configuration. Complex K1 crystallized as the pure diastereomer S_Ru, S_C4, R_C5. In solution epimerization S_Ru, S_C4, R_C5 ? R_Ru, S_C4, R_C5 occurred via change of the configuration at the ruthenium atom. The half‐life for the first‐order reaction at 0.4 °C in CD₂Cl₂ was 50.6 min. Thus, the two diastereomers equilibrate at room temperature. The equilibrium mixtures of K1 und K2 were used as catalysts for the transfer hydrogenation of acetophenone and for the Diels‐Alder reaction of cyclopentadiene with methacrolein. Enantiomeric excesses of up to 60 % ee were achieved.     

Polymorphism of Copper(I) Halide π‐Complexes: Synthesis and Structure of a New Modification of [Cu2Cl2(CH2=CH–CH2)2O]

A new polymorph of [Cu₂Cl₂(CH₂=CH–CH₂)₂O] has been obtained by an alternating‐current electrochemical synthesis starting from CuCl₂ and triallylphosphite. Diallylether was obtained in statu nascendi via transetherification of triallylphosphite. The structure is monoclinic, space group P2₁/n, a = 7.6738(7), b = 6.5128(4), c = 18.2689(18) Å, β = 91.644(11)°, V = 912.67(13) ų (at 150 K), Z = 4; R₁ = 0.0339, wR₂ = 0.0822. Flexibility of the organic ligand and weak interactions copper···halogen have been identified as the main reasons enabling polymorphism in molecular π‐complexes of copper(I).     

Acyl- und Alkylidenphosphane. XXXII [1, 2]. Di-cyclo-hexoyl- und Diadamant-1-oylphosphan — Keto-Enol-Tautomerie und Struktur

Acyl- and Alkylidenephosphines. XXXII. Di-cyclohexoyl- and Diadamant-1-oylphosphine – Keto-Enol Tautomerism and Structure Lithium dihydrogenphosphide · DME (¹) [12] and cyclo-hexoyl or adamant-1-oyl chloride react in a molar ratio of 3:2 to give lithium di-cyclo-hexoylphosphide · DME and the corresponding diadamant-1-oylphosphide.2THF (¹) resp. Treatment of these two compounds with 85% tetrafluoroboric acid. diethylether adduct yields di-cyclo-hexoyl- ( 1b ) and diadamant-1-oylphosphine ( 1c ). In nmr spectroscopic studies 1b over a range of 203 to 343 K, a strong temperature dependence of the keto-enol equilibrium is found; thermodynamic data characteristic for the formation of the enol tautomer (ΔH⁰ = ?4.3 kJ. mol^?1; ΔS⁰ = ?9.2 J. mol^?1. K (^?1) are compared of 1,3-diketones. The enol tautomer of diadamant-1-oylphosphine ( E-1c ) as obtained from a benzene solution in thin colourless plates, crystallizes in the monoclinic space group P2₁/c {a = 722.2(2); b = 1085.5(4); c = 2434.8(5) pm; ß = 96.43(2)° at –100 ± 3°C; Z = 4}. An X- ray structure analysis (R_w = 0.033) shows bond lengths and angles to be almost identical within the enolic system (P? C 179/180; C? O 130/129; C? C(adamant-1-yl) 152/153 pm; C? P? C 99°; P? C? O 124°/124°; P? C? C 120°/120°; C? C? O 116°/116°. The geometry of the very strong, but probably asymmetric O‥H‥O bridge is discussed (O? H 120/130, O‥O 245 pm).     

Chemischer Transport fester Lösungen. 9 [1] Zum Chemischen Transport fester Lösungen in den Systemen Eisen(II)/Cobalt(II)‐ und Mangan(II)/Cobalt(II)‐germanat

Metagerma‐Chemical Vapor Transport of Solid Solutions. 9. The Chemical Vapor Transport of Solid Solutions in the System Iron(II)/(Cobalt(II)‐and Manganese(II)/Cobalt(II) Germanate By means of chemical vapor transport methods (900 → 700 °C) using HCl as transport agent FeGeO₃, Fe₂GeO₄ and MnGeO₃ have been prepared. Co₂GeO₄ and Fe₂GeO₄ as well as CoGeO₃ and FeGeO₃ form continuous crystalline solid solutions, whereas in MnO/CoO/GeO₂ two different phases (Mn_xCo_1‐x)GeO₃ are formed. All of these systems show congruent transport behaviour. Chemical vapor transport has been proved a suitable method to prepare solid solutions.     

Alternativ-Liganden. XXXII [1]. Neue Tetraphosphan-Nickelkomplexe mit Tripod-Liganden des Typs XM′ (OCH2PMe2)n(CH2CH2PR2)3 – n (M′ = Si,Ge; n = 0 – 3)

Alternative Ligands. XXXII [1]. Novel Tetraphosphane Nickel Complexes with Tripod-Ligands of the Type XM′(OCH₂PMe₂)_n(CH₂CH₂PR₂)_{3 – n} (M′ = Si, Ge; n = 0 – 3) Tripod Ligands of the type XM′(OCH₂PMe₂)_n(CH₂CH₂PMe_{23 – n} (M′ = Si, Ge; n = 0 – 3) ( 1 – 6 , Table 1) have been used together with PPh₃ or PMe₃ for the preparation of novel tetraphosphane complexes of Nickel. The representatives LNiPPh₃ ( 7 – 12 ) are obtained by reaction of Ni(COD)₂ (COD = 1,5-cyclooctadiene) with the corresponding ligands and PPh₃ in toluene in moderate yields. The synthesis of the derivatives LNiPMe₃ ( 13 – 18 ) is partly ( 16 – 18 ) accomplished in analogy to the Ph₃P-complexes; compounds 13 – 16 are obtained in higher yields by reaction of Ni(PMe₃)₄ with the respective ligand. As a rule, 13 – 18 cannot be separated from by-products. The trinuclear complex FSi(CH₂CH₂PMe₂)₃[Ni(PMe₂CH₂CH₂)₃SiF]₃ ( 19 ) is formed together with 18 in the reaction of Ni(COD)₂ with 6 and PMe₃. The new compounds have been characterized (if possible) by analytical (C, H), but in general by spectroscopic investigations (IR; ¹H-, ¹³C-, ¹⁹F-, ³¹P-NMR; MS). A weak, but significant Ni → Si interaction through the cage is indicated by the following results: (i) Large low-field shifts δδ_F of 35.2 ppm ( 12 ), 38.3 ppm ( 18 ) and 37.7 ppm ( 19 ); (ii) ⁶J(PF) coupling constants [or ³J(PNiSiF) through the cage] of 6.0 Hz ( 12 ) and 7.6 Hz ( 18 ) together with a low-field shift δδ_Si of 12.8 ppm ( 12 ); (iii) NiSi distances of 3.95 Å in 7 and 3.92 Å in 12 , accompanied by a compression of the cage along the Ni ··· Si axis. An additional release from the high charge density on Ni results from π-backbonding to the phosphane ligands.     

Copper(I) π‐Complexes with 2‐Butyne‐1,4‐diol. Synthesis and Crystal Structure of Na[CuCl2(HOCH2C≡CCH2OH)]·2H2O

Crystals of anionic Na[CuCl₂(HOCH₂C≡CCH₂OH)]·2H₂O π‐complex have been synthesized by interaction of 2‐butyne‐1,4‐diol with CuCl in a concentrated aqueous NaCl solution and characterized by X‐ray diffraction at 100 K. The crystals are triclinic: space group , a = 7.142(3), b = 7.703(3), c = 10.425(4) Å, α = 105.60(3), β = 99.49(3), γ = 110.43(3)°, V = 495.9(4) ų, Z = 2, R = 0.0203 for 3496 reflections. The structure is built of discrete [CuCl₂(HOCH₂C≡CCH₂OH)]^? anionic stacks and polymeric cations among the stacks. The Cu^I atom adopts trigonal planar coordination of two Cl^? anions and the C≡C bond of 2‐butyne‐1,4‐diol, Cu–(C≡C) distance is equal to 1.903(3) Å. Na⁺ cations environment is octahedral and consists of O and Cl atoms. The crystal packing is governed by strong hydrogen bonds of O–H···Cl and O–H···O types.     

1:1 Adducts of Copper(I) and Silver(I) Halides with the Olefinic Phosphane Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane. Molecular Structures of CuX[P(C7H7)3] (X = Cl,Br), AgCl[P(C7H7)3] and {Cu(μ3‐I)[P(C7H7)3]}4

A suspension of CuX (X = Cl, Br) or AgCl in organic solvents (such as CH₂Cl₂) reacts with P(C₇H₇)₃ ( 1 ) in a molar ratio 1:1 to give the mononuclear adducts CuX[P(C₇H₇)₃] (X = Cl ( 2a ), Br ( 2b )) and AgCl[P(C₇H₇)₃] ( 3a ) which crystallize as isotypic compounds in the orthorhombic space group Pnma (Z = 4). In the crystal, two (of the three) cyclohepta‐2, 4, 6‐trienyl substituents are present in the boat conformation, thus establishing a loose long‐distance interaction between the central double bond and the metal atom. A distorted pseudo‐tetrahedral coordination sphere is assumed to exist around the metal atom, with large P‐M‐X angles of 165.49(8)° ( 2a ), 162.07(7)° ( 2b ) and 168.54(3)° ( 3a ), respectively. The tetrameric 1:1 adduct {Cu(μ₃‐I)[P(C₇H₇)₃]}₄( 2c ) which was obtained from CuI and 1 in boiling ethanol, has also been characterized by X‐ray crystallography (monoclinic space group P2(1)/n, Z = 4); it contains all 12 cyclohepta‐2, 4, 6‐trienyl substituents in the chair conformation. The NMR spectra (¹H, ¹³C, ³¹P) of the new complexes 2a‐c and 3a indicate non‐rigid structures in solution. At room temperature, the ³¹P NMR signal of 3a appears as a doublet with an averaged coupling constant, ¹J(Ag, P), of 700.1 Hz, whereas at —45 °C the two expected doublets are clearly discernible with coupling constants ¹J(¹⁰⁷Ag, ³¹P) = 671.0 Hz and ¹J(¹⁰⁹Ag, ³¹P) = 774.4 Hz, respectively.     

Polysulfonylamine. LXI [1]. Silber(I) in einer neuartigen N-Donor-Umgebung: Darstellung und Struktur von catena-Poly[(dimesylamido-N)(acetonitril)(μ-pyrazin)silber(I)]

Polysulfonyl Amines. LXI. Silver(I) in a Novel N-Donor Environment: Synthesis and Structure of catena-Poly[(dimesylamido-N)(acetonitrile)(μ-pyrazine)silver(I)] The complex [Ag{N(SO₂Me)₂}(μ-pz)(MeCN)]_∞ is precipitated upon adding pyrazine to an acetonitrile solution of AgN(SO₂Me)₂. Crystallographic data (at ?100°C); monoclinic, space group P2₁/c, a = 912.3(2), b = 1 396.5(3), c = 1 151.7(3) pm, β = 97.20(2)°, U = 1.4557 nm³, Z = 4. The structure consists of infinite zigzag chains in the z-direction. The chain backbone is composed of silver atoms linked by pyrazine ligands (N? Ag? N 99.4°, Ag? N 232.4 und 234.0 pm). The severely distorted tetrahedral environment of Ag is completed by an N-bonded dimesylamide anion (Ag? N 224.3 pm) and an acetonitrile molecule (Ag? N 240.9 pm). The N? Ag? N angles vary from 97.5 bis 125.7°.     

Einkristall-Röntgenstrukturanalysen an Verbindungen mit kovalenter Metall—Metall-Bindung. II. Die Molekül- und Kristallstruktur von X2Sn[Mn(CO)5]2 (XCl,Br) Verbindungen

Single Crystal X-Ray Analysis of Compounds with Covalent Metal–Metal Bonds. II. Molecular and Crystal Structure of X₂Sn[Mn(CO)₅]₂ (X?Cl, Br) Both X₂Sn[Mn(CO)₅]₂ compounds (X?Cl, Br) crystallize in the monoclinic crystal system with at times different values in the lattice parameters. They belong to the space group C_2h⁵. The structures have been solved using 2 107 symmetrical independent reflection for Cl₂Sn[Mn(CO)₅]₂ and 1 470 reflections for Br₂Sn[Mn(CO)₅)₂] by applying the heavy atom method. The following interatomic distances have been found: Cl₂Sn[Mn(CO)₅]₂, Sn? Mn = 2.635(1) Å, Sn? Cl = 2.385(2) Å, Mn? C = 1.852(8) Å, C? O = 1.128(10) Å; Br₂Sn[Mn(CO)₅]₂, Sn? Mn = 2.642(3) Å, Sn? Br = 2.548(2) Å, Mn? C = 1.851(21) Å, C? O = 1.124(25) Å. In addition, bond angles of X? Sn? X and Mn? Sn? Mn of these compounds have also been estimated in the case of X = Cl: 95.80(7)° and 126.25(4)° and for X?Br: 98.44(8)° and 125.88(9)°. The individual molecules of the X₂Sn[Mn(CO)₅]₂ solids are surrounded by ligands showing distorted tetrahedral configuration at the Sn atom and distorted octahedral configuration at the Mn atom.     

Zur Reaktion der Alkin‐Kupfer(I)‐Komplexe [CuX(S‐Alkin)] (X = Cl,Br, I; S‐Alkin = 3,3,6,6‐Tetramethyl‐1‐thia‐4‐cycloheptin) mit den Phosphanen PMe3 und Ph2PCH2CH2PPh2 (dppe)

Organometallic Compounds of Copper. XVIII. On the Reaction of the Alkyne Copper(I) Complexes [CuX(S‐Alkyne)] (X = Cl, Br, I; S‐Alkyne = 3,3,6,6‐Tetramethyl‐1‐thiacyclohept‐4‐yne) with the Phosphanes PMe₃ and Ph₂PCH₂CH₂PPh₂ (dppe) The alkyne copper(I) halide complexes [CuX(S‐Alkyne)]_n ( 2 ) ( 2 a : X = Cl, 2 b : X = Br, 2 c : X = I; S‐Alkyne = 3,3,6,6‐tetramethyl‐1‐thiacyclohept‐4‐yne; n = 2, ∞) add the phosphanes PMe₃ and Ph₂PCH₂CH₂PPh₂ (dppe) to form the mono‐ and dinuclear copper compounds [(S‐Alkyne)CuX(PMe₃)] ( 6 ) ( 6 a : X = Cl, 6 b : X = Br) and [(S‐Alkyne)CuX(μ‐dppe)CuX(S‐Alkyne)] ( 7 a : X = Cl, 7 b : X = Br, 7 c : X = I), respectively. By‐product in the reaction of 2 a with dppe is the tetranuclear complex [(S‐Alkyne)Cu(μ‐X)₂Cu(μ‐dppe)₂Cu(μ‐X)₂Cu(S‐Alkyne)] ( 8 ). In case of the compounds 7 prolonged reaction times yield the alkyne‐free dinuclear copper complexes [Cu₂X₂(dppe)₃] ( 9 ) ( 9 a : X = Cl, 9 b : X = Br, 9 c : X = I)). X‐ray diffraction studies were carried out with the new compounds 6 a , 6 b , 7 b , 8 , and 9 c .     

Metallorganische Lewis-Säuren. XLII. Carbonyl- und Nitrosyl-Komplexe von Mangan und Rhenium mit schwach koordinierten Anionen (Ph3P)2(ON)2MnX, (Ph3P)n(OC)5–nMX (M = Mn,Re; n = 1, 2; X = FBF3, OSO2CF3, OSO2F,OCORf)

Organometallic Lewis Acids. XLII. Carbonyl- and Nitrosyl Complexes of Manganese and Rhenium of Weakly Coordinated Anions (Ph₃P)₂(ON)₂MnX, (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃, OSO₂F, OCOR_f) The complexes (Ph₃P)₂(ON)₂MnX (X = FBF₃, OSO₂CF₃, OSO₂F, OCOCF₃, OCOC₃F₇) and (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃) have been obtained by reaction of (Ph₃P)₂(ON)₂MnH and (Ph₃P)_n(OC)_5–nMeMe with the corresponding acids HX or from (Ph₃P)_n(OC)_5–nReBr (n = 1, 2) with silver salts AgX, respectively. The compounds have been characterized by their IR and partially by ¹⁹F-NMR data. An efficient method for the preparation of the hydride (Ph₃P)₂(ON)₂MnH is reported.     

Synthesis and Characterization of New Copper(I) Complexes Containing Thione Derivatives of 1, 2, 4‐Triazine. Crystal Structure of [Cu(PPh3)2(ATTO)]NO3 (ATTO = 4‐amino‐1, 2, 4‐triazin‐3(2H)‐thione‐5‐one)

The reaction of 4‐amino‐1, 2, 4‐triazin‐3(2H)‐thione‐5‐one (ATTO, 1 ) with [Cu(PPh₃)₂]NO₃ in ethanol led to the complex [Cu(PPh₃)₂(ATTO)]NO₃ ( 2 ). 2 was characterized by elemental analyses, IR, ¹H NMR and Raman spectroscopy. A single‐crystal X‐ray diffraction of compound 2 revealed that ATTO acts as a bidentate ligand via its nitrogen and sulfur atoms. Crystal data for 2 at 20 °C: space group P2₁/n with a = 975.7(1), b = 1533.5(2), c = 2504.2(3) pm, β = 92.25(1)°, Z = 4, R₁ = 0.0632.     

Chemischer Transport fester Lösungen. 10 [1] Zum Chemischen Transport von quaternären Cobalt(II)‐Zink‐ und Mangan(II)‐Zinkgermanaten

Chemical Vapor Transport of Solid Solutions 10 [1] The Chemical Vapor Transport of quarternary Cobalt(II)‐Zinc and Manganese(II)‐Zinc Germanates By means of chemical vapor transport methods using HCl or Cl₂ as transport agent the crystalline solid solutions (Zn_xCo_1—x)₂GeO₄ and (Mn_xZn_1—x)₂GeO₄ have been prepared (1050 → 900 °C, 850 → 700 °C, respectively). ZnGeO₃ — although unknown as a pure solid — can be stabilized as a mixed crystal (Mn_xZn_1—x)GeO₃ (x > 0, 5).     

[1‐Allylpyridinium][Cu2Cl3]: Synthesis,X‐ray Structure and the Regularity of Crystal Architecture of 1‐Allyl/(amino)‐pyridinium Copper(I) Chloride π‐Complexes

By alternating‐current electrochemical technique crystals of copper(I) π‐complex with 1‐allylpyridinium chloride of [C₅H₅N(C₃H₅)][Cu₂Cl₃] ( 1 ) composition have been obtained and structurally investigated. Compound 1 crystallizes in monoclinic system, space group C2/c a = 24.035(1) Å, b = 11.4870(9) Å, c = 7.8170(5) Å, β = 95.010(5)°, V = 2150.0(2) ų (at 100 K), Z = 8, R = 0.028, for 4836 independent reflections. In the structure 1 trigonal‐pyramidal environment of π‐coordinated copper(I) atom is formed by a lengthened to 1.376(2) Å C=C bond of allyl group and by three chlorine atoms. Other two copper atoms are tetrahedrally surrounded by chlorine atoms only. The coordination polyhedra are combined into an original infinite (Cu₄Cl₆^2—)_n fragment. Structural comparison of 1 and the recently studied copper(I) chloride π‐complexes with 3‐amino‐, 2‐amino‐, 4‐amino‐1‐allylpyridinium chlorides of respective [LCu₂Cl₃] ( 2 ), [L₂Cu₂Cl₄] ( 3 ), and [LCuCl₂] ( 4 ) compositions allowed us to reveal the trend of the inorganic fragment complication which depends on pKa (base) value of the corresponding initial heterocycle.     

Cob(I)alamin als Katalysator, 5. Mitteilung [1]. Enantioselektive Reduktion α,β-ungesättigter Carbonylderivate

Cob(I)alamin as Catalyst. 5. Communication [1]. Enantioselective Reduction of α,β-Unsaturated Carbonyl Derivatives The cob(I)alamin-catalyzed reduction of an α,β-unsaturated ethyl ester in aqueous acetic acid produced the (S)-configurated saturated derivative 2 with an enantiomeric excess of 21%. The starting material 1 is not reduced at pH = 7.0 in the presence of catalytic amounts of cob(I)alamin (see Scheme 2). It is shown that the attack of cob(I)alamin and not of cob(II)alamin, also present in Zn/CH₃COOH/H₂O, accounts for the enantioselective reduction observed. All the (Z)-configurated starting materials 1 , 3 , 5 , 7 , 9 and 11 have been transformed to the corresponding (S)-configurated saturated derivatives 2 , 4 , 6 , 8 , 10 and 12 , respectively. The highest enantiomeric excess revealed to be present in the saturated product 12 (32,7%, S) derived from the (Z)-configurated methyl ketone 11 (see Scheme 3 and Table 1). The reduction of the (E)-configurated starting materials led mainly to racemic products. A saturated product having the (R)-configuration with a rather weak enantiomeric excess (5.9%) has been obtained starting from the (E)-configurated methyl ketone 23 (see Scheme 5 and Table 2). The allylic alcohols 16 and 24 have been reduced to the saturated racemic derivative 17 .     

Non‐Isomorphic Chlorine—Bromine Substitution in the Copper(I) Halide π‐Complexes with 1‐Allyl‐4‐aminopyridinium

By alternating‐current electrochemical synthesis crystals of {Cu[H₂NC₅H₄N(C₃H₅)]Br₂} ˙ H₂O ( I ), {Cu[H₂NC₅H₄N(C₃H₅)]Br_0.65Cl_1.35} ˙ H₂O ( II ) and {Cu[H₂NC₅H₄N(C₃H₅)]Cl₂} ( III ) π‐complexes have been obtained and structurally investigated. The I and II compounds are isostructural and crystallize in a monoclinic sp. gr. P2₁/c, I : a = 7.359(2)Å, b = 12.3880(6)Å, c = 13.637(3)Å, β = 107.03(1)°, V = 1188.7(4)ų, Z = 4 for C₈H₁₃N₂OBr₂Cu composition, R = 0.0293 for 2140 reflections. II : a = 7.2771(6)Å, b = 12.3338(3)Å, c = 13.4366(7)Å, β = 107.632(2)°, V = 1149.3(1)ų, Z = 4 for C₈H₁₃N₂Br_0.65Cl_1.35Cu composition, R = 0.0463 for 2185 reflections. Metal and halogen atoms form centrosymmetric Cu₂X₄ dimers. Each copper atom is surrounded by three halogen atoms and by a weakly bonded C=C‐group of the onium moiety. Isolated {Cu[H₂NC₅H₄N(C₃H₅)]}₂X₄ dimers are combined into a three‐dimensional network due to a bridging function of water molecules via a system of rather strong hydrogen bonds. Chlorine derivative III crystallizes in another structure type: sp. gr. C2/c, a = 21.568(7)Å, b = 7.260(2)Å, c = 13.331(3)Å, β = 95.65(2)°, V = 2077(2)ų, Z = 8 for C₈H₁₁N₂Cl₂Cu composition. Copper atom, included in CuCl₂^— isolated fragment, is coordinated to a C=C‐bond of ligand moiety. N‐H…Cl hydrogen bonds unite Cu[H₂NC₅H₄N(C₃H₅)]Cl₂ subunits into infinite ribbons. π‐Interaction in III appears to be more effective than in I and II .     

Photoelektronen-Spektren und Moleküleigenschaften. 132 [1, 2]. Trifluormethylsulfan und Derivate F3CSX (X  CF3, Cl,Br, I)

Photoelectron Spectra and Molecular Properties. 132. Trifluoromethylsulfane and Derivatives F₃CSX (X ? CF₃, Cl, Br, I) The He(I) photoelectron spectra of trifluoromethylsulfane F₃CSH and its derivatives F₃CSX (X ? CF₃, Cl, Br, I) are assigned by Koopmans' correlations, IE = ?ε, with MNDO eigenvalues, by radical cation state comparison and based on resolved vibrational fine structures, which can' be discussed by MNDO FORCE calculations. The spin/orbit splitting in F₃CSI can be approximated by additional ITEREX-85 calculations. Gasphase thermolysis of the trifluoromethylhalogensulfanes F₃CSX at 10^?4 mbar yields decomposition temperatures, which decrease from X ? Cl to I, and as fragmentation products of presumably radical intermediates, in addition to the respective halogens X₂ and F₂C?S, also F₃CX as well as S₂ and CS₂ (X ?Cl, Br) are PE spectroscopically detected.