Fritjof Schmock

Metallorganische diazoalkane : IV. Organoquecksilber-diazoketone

Abstract The preparations of organomercury diazoketones RHgC(N2)C(O)R′ and of Hg[C(N2C(O)R′]2, with RCH3, C2H5, R′CH3, C6H5, are described and the spectroscopic properties of the derivatives are reported on the basis of their IR/Raman, 1H NMR and mass spectra.

[In3Br3{C(SiMe3)3}3][Li(THF)3] mit einer Kette aus drei Indiumatomen — ein bemerkenswertes Nebenprodukt aus der Synthese des Tetraindiumclusters In4[C(SiMe3)3]4

Durch Umsetzung von Indiummonobromid mit dem Tetrahydrofuran-Addukt der Lithiumverbindung LiC(SiMe3)3 gelingt die einfache Synthese der tief violetten Tetraindiumverbindung In4[C(SiMe3)3]4 (1), die uber einen tetraedrischen Cluster aus vier einwertigen Indiumatomen verfugt. Dabei entsteht in grosen gelben Kristallen als Nebenprodukt [In3Br3{C(SiMe3)3}3]— [Li(THF)3]+ (2), dessen Konstitution wir jetzt aufklarten. 2 bildet eine Kette aus drei durch InIn-Einfachbindungen miteinander verbundenen Indiumatomen, von denen die beiden terminal angeordneten durch zwei Bromatome verbruckt werden. Das mittlere Indiumatom bindet an ein Bromidion, das eine Bruckenposition zum Gegenion [Li(THF)3]+ einnimmt. [In3Br3{C(SiMe3)3}3][Li(THF)3] with a Chain of Three Indium Atoms — a Remarkable By-product of the Synthesis of the Tetraindium Cluster In4[C(SiMe3)3]4 The reaction of indium bromide InBr with the THF adduct of LiC(SiMe3)3 afforded the deep violet tetraindium compound In4[C(SiMe3)3]4 (1) which possesses a tetrahedral cluster of four monovalent indium atoms. A yellow by-product was isolated and identified now as the compound [In3Br3{C(SiMe3)3}3]— [Li(THF)3]+ (2). 2 has a chain of three indium atoms connected by In-In single bonds. The terminal indium atoms are bridged by two bromine atoms, and the inner indium atom is attached to a bromide ion which bridges the In3 chain and the counter ion [Li(THF)3]+.

Die Kristallstrukturen der Azido‐Platinate (AsPh4)2[Pt(N3)4] und (AsPh4)2[Pt(N3)6]

Die Kristallstrukturen der beiden homoleptischen Azido-Platinate (AsPh4)2[Pt(N3)4] (1) und (AsPh4)2[Pt(N3)6] (2) wurden rontgenographisch an Einkristallen ermittelt. In 1 sind die [Pt(N3)4]2–-Ionen ohne kristallographische Lagesymmetrie und die Platin-Atome weisen planare Umgebung auf. Die [Pt(N3)6]2–-Ionen in 2 sind zentrosymmetrisch (Ci) mit oktaedrischer Umgebung an den Platin-Atomen. Wahrend 1 brisant ist, hat 2 eine deutlich grosere Stabilitat. Dieses Verhalten wird durch die Packungsverhaltnisse erklart. 1: Raumgruppe P21/n, Z = 6, Gitterkonstanten bei –80 °C: a = 1045,3(1); b = 1620,2(1); c = 4041,0(3) pm; β = 96,70(1)°; R1 = 0,0654. 2: Raumgruppe P1, Z = 1, Gitterkonstanten bei –80 °C: a = 1027,6(1); b = 1049,1(2); c = 1249,9(3) pm; α = 88,27(1)°; β = 74,13(1)°; γ = 67,90(1)°; R1 = 0,0417. Crystal Structures of the Azido Platinates (AsPh4)2[Pt(N3)4] and (AsPh4)2[Pt(N3)6] The crystal structures of the two homoleptic azido platinates (AsPh4)2[Pt(N3)4] (1) and (AsPh4)2[Pt(N3)6] (2) were determined by X-ray diffraction at single crystals. In 1 the [Pt(N3)4]2– ions are without crystallographic site-symmetry, and the platinum atoms show a planar surrounding. The [Pt(N3)6]2– ions in 2 are centrosymmetric (Ci) with an octahedral surrounding at the platinum atoms. While 1 is highly explosive, 2 is of significantly greater stability. This behaviour is explained by the packing conditions. 1: Space group P21/n, Z = 6, lattice dimensions at –80 °C: a = 1045.3(1), b = 1620.2(1), c = 4041.0(3) pm; β = 96.70(1)°; R1 = 0.0654. 2: Space group P1, Z = 1, lattice dimenstions at –80 °C: a = 1027.6(1), b = 1049.1(2), c = 1249.9(3) pm; α = 88.27(1)°, β = 74.13(1)°, γ = 67.90(1)°; R1 = 0.0417.

(Ph4P)S6—A Compound Containing the Cyclic Radical Anion S6.−

Two long S−S bonds link the two S3 fragments in the cyclic radical anion S6.−. This forms as orange‐red crystals with PPh4+ as the counterion in the reaction of sulfane with (tetraphenylphosphonium) hydrogen diazide. The anion has a chair conformation with C2h symmetry (see picture).

(Ph4P)S6 – eine Verbindung mit dem cyclischen Radikalanion S6.−

Uber zwei lange S‐S‐Bindungen sind die beiden S3‐Fragmente im cyclischen Radikalanion S6.− verbunden. Dieses entsteht bei der Reaktion von Sulfan mit (Tetraphenylphosphonium)hydrogendiazid in Form orangeroter Kristalle mit Ph4P+ als Gegenion. Experimentell wurde fur das Anion eine Sesselkonformation mit der Symmetrie C2h gefunden (siehe Bild).

Synthese, IR-Spektrum und Kristallstruktur von 1.3.5-Trichlortriazinium-hexachloroantimonat, [HC3N3Cl3]SbCl6 / Synthesis, IR Spectrum and Crystal Structure of 1.3.5-Trichlortriazinium Hexachloroantimonate, [HC3N3Cl3]SbCl6

Abstract 1,3,5-Trichlortriazinium hexachloroantimonate has been prepared by the reaction of CCl2 = N-COCl with antimony pentachloride in boiling dichloromethane. The compound was characterized by IR spectroscopy and by a crystal structure determination. [HC3N3Cl3]SbCl6 crystallizes in the monoclinic space group P21/n with four formula units per unit cell. 2503 observed unique reflections, R = 0.029. Lattice dimensions at 19 °C: a = 1314.1(1), b = 958.2(1), c = 1329.1(1) pm, β = 117.113(5)°). The compound forms ion pairs via a linear N-H ··· Cl bridge, thus distorting the SbCl6- ion from octahedral geometry. The C3N3 skeleton of the [HC3N3Cl3]+ ion is nearly planar, but the hydrogen atom lies about 30 pm out of this plane.

Synthese und Kristallstruktur von 2-Trimethylsilyl-1,3-bistrimethylsilylimino-1,3-dihydro-isoindol sowie die Kristallstruktur von Hexakis(trimethylsilyl)-1,4-benzdiamidin / Synthesis and Crystal Structure of 2-Trimethylsilyl-1,3-bis-trimethylsilylimino-1,3-dihydro-isoindole and the Crystal Structure of Hexakis(trimethylsilyl)-1,4-benzdiamidine

2-Trimethylsilyl-1,3-bis-trimethylsilylimino-1,3-dihydro-isoindole, C8H4N3(SiMe3)3 (2), has been prepared by the reaction of 1,2-benzodinitrile with LiN(SiMe3)2, followed by treatment with ClSiMe3. 2 forms yellow crystals, which were characterized by a crystal structure determination, as was the known hexakis(trimethylsilyl)-1,4-benzdiamidine, {[(SiMe3)2N](SiMe3N)C-C6H4-C(NSiMe3)[N(SiMe3)2]}) (1). 1: space group P1, Z = 1̄,2520 observed independent reflexions, R = 0.052. Lattice dimensions (19°C): a = 662.7(1); b = 1088.3(1); c = 1417.4(2) pm; α = 76.60(1)°; β = 87.33(1)°; γ = 73.90(1)°. 1 forms monomeric centrosymmetric molecules with the amidino groups in 1,4-position of the C6H4 ring. The CN distances are 127.1(3) and 141.3(3) pm, respectively, corresponding to C=N̅-SiMe3 and C-N̅(SiMe3)2 moieties. 2: space group P212121, Z = 4, 1960 observed independent reflexions, R = 0.058. Lattice dimensions (20°C): a = 643.0(1); b = 1477.4(1); c = 2414.4(2) pm. 2 forms monomeric molecules with a planar isoindole skeleton with different Si-N-bond lengths of the SiMe3 groups in 2-position (180.2(5) pm) and in 1,3-positions (171.4(5); 170.9(9) pm).

Notizen: Synthese und Kristallstruktur von PPh3Me[HSO4]/ Synthesis and Crystal Structure of PPh3Me[HSO4]

Abstract PPh3Me[HSO4] was prepared by the reaction of (PPh3Me)I with silver sulfate in aqueous solution. OPPh2Me and benzene being the by-products. The title compound was characterized by its IR spectrum as well as by an X-ray structure determination (1730 observed independent reflexions, R = 0.043). Crystal data: a = 910.4(3). b = 1587.8(4), c = 1294.2(6) pm, β = 105.52(3)°. space group P21/c, Z = 4. The structure consists of PPh3Me⊕ cations and of HOSO3⊖ ions that are associated via strong hydrogen bonds to dimeric centrosymmetric units.

The NaCl adduct of the iron-indium compound Fe2(CO)6(μ-CO)(μ-InR)2 [R = C(SiMe3)3]: a one-dimensional coordination polymer with sodium oxygen bridges

The organoindium subhalide [R(Cl)In-In(Cl)R]2 [R = C(SiMe3)3] 1 reacts with Na2[Fe2(CO)8] to form an iron-indium coordination compound which was isolated as the sodium choride adduct [Na(THF)4][Fe2(CO)6(μ-CO)(μ-InR)2Cl] 2. The iron atoms of 2 are bridged by a CO ligand and two InR groups, the indium atoms of which are further connected by the μ2-bridging chlorine atom. Four THF molecules and two oxygen atoms of terminal CO ligands of different anions span the coordination sphere of the sodium cations to give a one-dimensional coordination polymer in the solid state.

Die Kristallstruktur des Phosphaniminato-Komplexes [TiCl3(NPPh3)•TiCl4]2 / Crystal Structure of the Phosphorane Iminato Complex [TiCl3(NPPh3)•TiCl4]2

The title compound was prepared from Me3SiNPPh3 and an excess of titanium tetrachloride. It forms yellow-orange crystals, which were characterized by IR spectroscopy and by crystal structure determination. Space group P21/n, Z = 2; lattice dimensions at 20°C: a = 1189.2(1), b - 1718.5(1), c = 1238.1(1) pm, β = 93.363(7)°. The compound forms centrosymmetric dimers in which the titanium atoms are triply and doubly bridged by chlorine atoms to give face- and edgesharing octahedra, respectively. In the linear units [Ti]=N =PPh3 the Ti-N bond distance of 171.6(3) pm corresponds to a double bond.