Guido J. Reiß

Hydrogen bonded 1,10-diammoniodecane – an example of an organo-template for the crystal engineering of polymeric polyiodides

Using the rod-like 1,10-diammoniodecane (dadH2) as a template it is possible to synthesize and crystallize the two polyiodide compounds (dadH2)2I2[I3]2 (1) and dadH2[I3]2·I2·2H2O (2). Compound 1 crystallizes in the polar monoclinic space group P21 with eight iodine atoms and two all-trans conformated 1,10-diammoniodecanes in the asymmetric unit. The structure is built by the dications and the two iodide anions forming a hydrogen bonded framework in which channels contain the two crystallographically independent I3− anions. These I3− anions are interconnected via extremely weak I⋯I interactions to a one-dimensional polymer with the I3− units linked to each other. They do not form hydrogen bonds of reasonable strength to the host framework. Compound 2 crystallizes in the centrosymmetric space group P21/n. The 1,10-diammonioalkane cations are lying on centres of symmetry and are showing an all-trans conformation. These cations form a sub-structure that is built by hydrogen bonded ribbons of 1,10-diammoniodecanes and water molecules in the ratio 1∶2. These ribbons act as polymeric templates for the formation of a iodine–iodide framework. This anionic sub-structure is best described as a three-dimensional framework built by I2 molecules and I3− anions showing the habit of a herring-bone motif. Neglecting the weak I⋯I interactions of ca. 4 A the polyiodide framework can be separated into outstretched, Z-shaped [I3⋯I2⋯I3]2− sub-units lying on centres of symmetry. In the structures of the compounds 1 and 2 the 1,10-diammoniodecane cations form hydrogen bonded ring motifs that may be classified to Etters rules as R24(30) with the iodide anions in 1 and water molecules in 2 acting as hydrogen bond acceptors. The crystal structure of the 1,10-diaminodecane (3) has been determined. This ‘soft as butter’ material crystallizes in the centrosymmetric space group Pbca with the molecules lying on a centre of symmetry and shows nearly ideal all-trans conformation. Only weak N–H⋯N hydrogen bonds occur between neighbouring molecules to form a layered structure. The molecules are arranged in the ac plane to form a herring-bone motif with the building ring motifs classified according Etters rules with the symbol R44(30).

Photochemical reactions of transition metal organyl complexes with olefins Part 10. Light-induced formal [5+2] cycloadditions at manganese

Abstract Tricarbonyl-η 5 -2,4-dimethyl-2,4-pentadien-1-yl-manganese ( 1 ) forms upon UV irradiation in THF at 208 K solvent stabilized dicarbonyl-η 5 -2,4-dimethyl-2,4-pentadien-1-yl-tetrahydrofurane-manganese ( 2 ). With butynedioic acid dimethyl ester ( 3 ) and diphenylacetylene ( 5 ) complex 2 yields tricarbonyl-η 5 -1,2-dimethoxycarbonyl-4,6-dimethyl- cyclohepta-2,4-dien-1-yl-manganese ( 4 ) and tricarbonyl-η-4,6-dimethyl-1,2-diphenyl-cyclohepta-2,4-dien-1-yl- manganese ( 6 ) in a formal [5+2] cycloaddition. Addition of carbon monoxide and a 1,4-H shift completes the reaction. Propynoic acid methyl ester ( 7 ) forms the 2:1 adduct dicarbonyl-η 5:2 -1,3-dimethyl-6-methoxycarbonyl-6- ( E-2 ′-methoxycarbonylvinyl)-cyclohepta-2,4-dien-1-yl-manganese ( 8 ). The crystal and molecular structure of 8 was determined by X-ray structure analysis. The molecular structures of the complexes 4 and 6 were established by IR and NMR spectroscopy. Formation mechanisms of 4 , 6 and 8 are discussed. Crystal data for 8 : monoclinic space group P 2 1 / c , a =802.6(3), b =1136.6(1), c =8872.3(3) pm, β=93.14(2)°, V =1.705 nm 3 , Z =4.

Ligand Synthesis and Metal Complex Formation of 1,2,3-Triaminopropane

A series of linear primary polyamines H2N–CH2–(CH–NH2)n–CH2–NH2 (1 ≤ n ≤ 3) was prepared from the corresponding polyalcohols. The polyamines were isolated as HCl adducts and the acidity constants in aqueous solution were determined. The crystal structure of the fully protonated tetraamine (n = 2) was elucidated by an X-ray diffraction study. Complex formation of the triamine (n = 1) with Ni2+, Cu2+, Zn2+, Cd2+ was re-investigated in aqueous solution. The pH-dependent formation of a variety of species MxLyHz was established by potentiometric titrations and was compared with previous reports. The crystal structure of the Cu complex [CuL2]Cl2 exhibited a chain structure with a five-coordinate CuII centre in which two amino groups of the triamine ligands are coordinated to one Cu centre, while the third amino group of one of the ligands is bonded to a neighbouring Cu atom. The compound shows weak antiferromagnetic coupling interactions between the CuII centres within the chain.

Dimer oder nicht dimer, das ist hier die Frage: Zwei benachbarte I3 –--Ionen eingeschlossen in Hohlr¨aumen einer komplexen Wirtsstruktur

[Me(HO)2P-(CH2)10-P(O)OHMe]2[I3]2・MeHO(O)P-(CH2)10-P(O)OHMe (1) was synthesized and characterized by IR, Raman and NMR spectroscopy. Its structure was determined by singlecrystal X-ray diffraction (T = 100 K; space group P1̄). The structure consists of decane-1,10-diyl-bis- (methylphosphinic acid) molecules and the analogous mono-protonated cations in a ratio 1:2 connected with each other by strong O-H···O hydrogen bonds to form a two-dimensional network. Between these hydrogen-bonded layers, there are elongated cavities each containing two triiodide anions. The intermolecular I· · · I distance of the two enclosed triiodide anions is 3.6317(4) Å and should be considered as an interhalogen bonding interaction. Graphical Abstract Dimer oder nicht dimer, das ist hier die Frage: Zwei benachbarte I3 –--Ionen eingeschlossen in Hohlr¨aumen einer komplexen Wirtsstruktur

How realistic are alternating C–C-bond lengths in s-cis-1,3-butadiene transition metal complexes?

A crystallographic redetermination of bis(s-cis-1,3-butadiene)monocarbonylmanganese showed that the earlier reported C–C bond lengths of the butadiene fragments are probably artefacts caused by pseudo symmetry problems. The problems of pseudo symmetry have been solved and the correct absolute structure has been assigned during the refinement of the structure in the non-centrosymmetric tetragonal space group P21m. This redetermination yielded balanced C–C distances for the complexed butadiene fragments. The molecular structure of the title compound has also been investigated by DFT-quantum chemical calculations [Becke3LYP/6-31+G(d) (C, H, O); 6-31G(f) (Mn)]. The typical understanding of bonding of butadienes to transition metal complexes and the experimental geometric parameters are in impressive agreement with the quantum chemical calculations. The problems discussed can also be expanded to molecular structures of isotypical complexes and similar pentamethylcyclopentadienyl transition metal complexes that crystallise in the space group P21m with the molecules located on a C2v (mm2) site.

Photolysis of Tricarbonyl(η5-cyclohexadienyl)manganese in Tetrahydrofuran, Reactions with Cumulated Dienes

[Mn(η5-C6H7)(CO)3] (1) forms highly reactive [Mn(η5-C6H7)(CO)2(THF)] (2) upon UV irradiation in THF at 208 K. Solvent complex 2 reacts between 208 and 293 K with 1,1-disubstituted allenes C3H2RR′ [R, R′ = CH3, CH3 (A); CH3, C6H5 (B); C2H5, C6H5 (C); C6H5, C6H5 (D); OCH3, Si(CH3)3 (E)] to four different types of complexes: The [5+2] cycloadduct [Mn(η3:2-C9H9RR′)(CO)3] (3E), rearranged [5+2] cycloadducts [Mn(η3:2-C9H9RR′)(CO)3] (4B, 4C, 4D), 1:2 adducts [Mn(η3:2-C12H11R2R′2)(CO)3] (5A–5E), and the 1:3 adduct [Mn{η3:2:2-C15H13(CH3)6}(CO)2] (6A). The constitutions of the products were established by IR and NMR spectroscopy, as well as by C,H elemental analysis and mass spectrometry. The crystal and molecular structure of 6A was determined by X-ray structure analysis. A formation mechanism for the complexes is proposed.

Photochemische Reaktionen von Übergangsmetall-Organyl-Komplexen mit Olefinen, XVI [1]: Photochemisch induzierte Cycloadditionen von Diphenylacetylen an Tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)mangan / Photochemical Reactions of Transition Metal Organyl Complexes with Olefins, XVI [1]: Photochemically Induced Cycloadditions of Diphenylacetylene to Tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)manganese

Upon UV irradiation in THF at 208 K tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)- manganese (1) yields solvent stabilized, very reactive dicarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)(tetrahydrofuran)manganese (2), which reacts in situ with one or two molecules of diphenylacetylene (3) and yields four manganese complexes and 1,3-dimethyl-5,6-diphenyl-bicyclo[3.2.1]oct-2-ene-7-one (5), which were separated by HPL chromatography. In addition to tricarbonyl η5-4,6 -dimethyl-1,2-diphenyl-cyclohepta-2,4-dien-1-yl)manganese (4) formed by [5+2]cycloaddition and successive 1,4-H shift, tricarbonyl{ 1′,2′,5′-η-5-methyl-2,3 -diphenyl-5- (2′-methyl-4′,5′-diphenyl-penta-1′,4′-dien-1′,5′-diyl)cyclopent-2-en-1 -one-κ-O}manganese (6) is isolated with a ligand, formed from 2,4-dimethyl-2,4-pentadien-1-yl, two units of 3 and one carbon monoxide. The ligands of tricarbonyl{ 1-4,2′-η-4,6 -dimethyl-1,2-diphenyl-5-(E-1′,2′- diphenyl-vinylen)cyclohepta-1,3-diene}manganese (7), and tricarbonyl{η5-4,6 -dimethyl-1,2-diphenyl-7-(E-1′,2′-diphenyl-vinyl)cyclohepta-2,4-dien-1-yl}m anganese (8) are formed from 2,4-dimethyl-2,4-pentadien-1-yl and of two molecules of 3 each. The crystal and molecular structures of 5 and 6 have been determined by single crystal X-ray diffraction. 5 crystallizes in the triclinic space group P1̅ , a = 992.0(2) pm, b = 996.8(2) pm, c = 1021.0(2) pm, a = 77.67(3)°, β = 61.17(3)°, γ = 88.68(3)°. Complex 6 crystallizes also in the triclinic space group P1̅ ,a = 1023.2(2) pm, b - 1113.8(2) pm, c = 1567.9(3) pm, α = 82.88(3)°, β = 86.93(3)°, 7 = 63.53(3)°. The constitutions of 4, 7 and 8 were elucidated from the IR, NMR and mass spectra. Possible formation mechanisms for the compounds 4-8 are proposed. Complex 7 shows hindered rotations of two phenyl groups with different barriers of energy ΔG≠316 = 68.8 kJ/mol, „ΔH≠ = 67.9 ± 0.7 kJ/mol, ΔS≠ = -2 ± 2 J/mol · K and ΔG≠296 = 60.6 kJ/mol, ΔH≠ = 57.7 ± 1.0 kJ/mol, ΔS≠ = -10 ± 2 J/mol·K due to steric interactions.

Photochemische reaktionen von übergangsmetall-organyl-komplexen mit olefinen XI. Photochemisch induzierte CC-verknüpfung von tricarbonyl-η5-2,4-dimethyl-2,4-pentadien-1-yl-mangan mit 1-dimethylamino-2-propin—Synthese eines η5-7-dimethylamino-N-2,4-heptadien-1-yl-chelatkomplexes

Abstract UV irradiation of tricarbonyl-η5-2,4-dimethyl-2,4-pentadien-1-yl-manganese (2) in THF at 208 K yields solvent-stabilized dicarbonyl-η5-2,4-dimethyl-2,4-pentadien-1-yl-tetrahydrofurane-manganese (3), which reacts in situ with two equivalents of 1-dimethylamino-2-propyne (4) to dicarbonyl-1–5-η-2,4-dimethyl-(6-dimethylaminomethyl-N)-10-dimethylamino-deca-2,4,6,8- tetraen-1-yl-manganese (5). The crystal and molecular structure was determined by an X-ray diffraction analysis. Complex 5 crystallizes in the monoclinic space group P21/c, a = 1109.9(2) pm, b = 836.0(2) pm, c = 2156.9(4) pm, β = 93.23(3)°, V = 1.9982(7) nm3, Z = 4. Complex 5 was also studied in solution by IR and NMR spectroscopy. A possible formation mechanism of 5 will be discussed.

Crystal Engineering of a New Layered Polyiodide Using 1,9-Diammoniononane as a Flexible Template Cation

Abstract The reaction of 1,9-diaminononane with hydroiodic acid in the presence of iodine gave a compound best described as 1,9-diammoniononane bis-triiodide iodine, (H3N-(CH2)9-NH3)[I3]2 · I2. The structure is built from two crystallographically independent I3− anions, which are connected via secondary I···I interactions to the iodine molecules, and the 1,9-diammonioalkane cations are connected via weak hydrogen bonds to neighbouring iodine atoms. By a cooperative phenomenon, the shape and the functionality of the cation lead to a solid state structure that includes a polyiodide substructure with the formula 2∞[I8]2− or 2∞[I3 · I2 · I3]2−, is best described as a brick-shaped layered array. Its rectangular pores fit excellently with the hydrogen bonding functionality as well as with the conformational needs of the 1,9-diammoniononane template. The Raman spectrum shows typical bands of coordinated triiodide anions and iodine molecules. The thermal analysis (DSC/TG) of the title compound indicates decomposition at temperatures above 210°C.

[Bi2(O2CCF3)4]⋅C6Me6 – ein Aren‐Addukt eines reduzierten Hauptgruppenelementcarboxylats mit Schaufelradstruktur

Der erste Hauptgruppen-Dimetallkomplex mit tetragonal-prismatischer Koordination ist [Bi2(O2CCF3)4] (Struktur siehe Bild), der mit Hexamethylbenzolmolekulen lineare, unendlich ausgedehnte Ketten bildet. Die von Chrom(II)-acetat und hunderten weiterer Ubergangsmetallkomplexe bekannte „Schaufelradstruktur” ist damit auch im Bereich der Hauptgruppenelementchemie eingefuhrt.