Hartmut Ackermann

[Mo2(O2C–CH3)4 · 1/2 {(CH2)6N4} · 1/2 CH2Cl2] – ein Donor‐Akzeptor‐Komplex mit supramolekularer Struktur

[Mo2(O2C–CH3)4 · 1/2 {(CH2)6N4} · 1/2 CH2Cl2] – a Donor-Acceptor Complex with Supramolecular Structure Yellow single crystals of [Mo2(O2C–CH3)4 · 1/2 {(CH2)6N4} · 1/2 CH2Cl2] (1) have been obtained by the reaction of the silylated phosphaneimine Me3SiNPEt3 with [Mo2(O2C–CH3)4] in dichloromethane solution. 1 forms a three-dimensional network with linear N–Mo:Mo–N and tetrahedral (CH2)6N4Mo4 moieties, which is topologically related with the PtS type. Space group P42/nnm, Z = 4, lattice dimensions at –70 °C: a = b = 1121.7(1), c = 1395.0(3) pm, R1 = 0.0413.

Synthese und Kristallstruktur des Aminoimino-Phosphinat–Kupfer(I)-Komplexes [Cu(Me3SiNP(Ph)2NSiMe3)]2

Synthesis and Crystal Structure of the Aminoiminophosphinate Copper(I) Complex [Cu(Me3SiNP(Ph)2NSiMe3)]2 The title compound 1 was prepared by the reaction of Me3SiNP(Ph)2N(SiMe3)2 with copper(I) chloride at 120 °C to give colourless crystals which were characterized by a crystal structure determination. Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1854.0(3), b = 1256.2(3), c = 1969.9(3) pm, β = 106.30(2)°; R1 = 0.063. 1 forms dimeric molecules with a nonplanar Cu2N4P2 eight-membered ring of symmetry C2 and a rather long Cu…Cu distance of 262.1(1) pm.

Phosphaniminato-Acetato-Komplexe von Cobalt und Cadmium mit M4N4-Heterocuban-Struktur

Die Phosphaniminato-Acetato-Komplexe [M(NPEt3)(O2C–CH3)]4 mit M = Co und Cd werden aus den wasserfreien Metall(II)acetaten mit uberschussigem Me3SiNPEt3 bei 180 °C gebildet. Durch Kristallisation aus Diethylether lassen sich blaue, feuchtigkeitsempfindliche Einkristalle von [Co(NPEt3)(O2C–CH3)]4 erhalten, wahrend farblose Einkristalle von [Cd(NPEt3)(O2C–CH3)]4 · 2 CH2Cl2 aus Dichlormethan-Losung entstehen. Im Vakuum wird das eingelagerte CH2Cl2 abgegeben. Die Komplexe werden durch die IR-Spektren und durch Kristallstrukturanalysen charakterisiert. In beiden Komplexen sind die Metallatome uber μ3–N-Brucken der (NPEt3–)-Gruppen zu Heterocubanen assoziiert. Im Cobalt-Komplex sind die Acetato-Liganden mit je einer kurzen Co–O- und einer langen Co–O-Bindung semichelatartig gebunden (Co–O-Abstande im Mittel 199,5 und 257,4 pm). Im Cadmium-Komplex bilden die Acetato-Gruppen nahezu symmetrische Chelate aus (Cd–O-Abstande im Mittel 232,1 und 237,8 pm), was zu verzerrt trigonal-bipyramidaler Anordnung an den Cd-Atomen fuhrt. [Co(NPEt3)(O2C–CH3)]4: Raumgruppe P 1, Z = 4, Gitterkonstanten bei –60 °C: a = 1110,1(2); b = 2051,3(5); c = 2169,5(4) pm; α = 100,03(2)°; β = 103,404(15)°; γ = 97,63(2)°; R = 0,0480. [Cd(NPEt3)(O2C–CH3)]4 · 2 CH2Cl2: Raumgruppe C2/c, Z = 4, Gitterkonstanten bei –80 °C: a = 1550,2(1); b = 2101,1(1); c = 1706,1(1) pm; β = 91,09(1)°; R = 0,0311. Phosphoraneiminato-Acetato Complexes of Cobalt and Cadmium with M4N4 Heterocubane Structure The phosphoraneiminato-acetato complexes [M(NPEt3)(O2C–CH3)]4 with M = Co and Cd are formed from the anhydrous metal(II) acetates with excess Me3SiNPEt3 at 180 °C. By crystallization from diethyl ether blue, moisture sensitive single crystals of [Co(NPEt3) · (O2C–CH3)]4 can be obtained, while colourless single crystals of [Cd(NPEt3)(O2C–CH3)]4 · 2 CH2Cl2 originate from dichloromethane solution. In vacuo the intercalary CH2Cl2 is released. The complexes are characterized by their IR spectra and by crystal structure analyses. In both complexes the metal atoms are associated via μ3–N bridges of the (NPEt3–) groups to form heterocubanes. In the cobalt complex the acetato ligands are bonded in a semichelate fashion with a short Co–O and a long Co–O bond each (Co–O distances in average 199.5 and 257.4 pm). In the cadmium complex the acetato groups form almost symmetrical chelates (Cd–O distances in average 232.1 and 237.8 pm); this leads to a distorted trigonal-bipyramidal arrangement at the cadmium atoms. [Co(NPEt3)(O2C–CH3)]4: Space group P 1, Z = 4, lattice dimensions at –60 °C: a = 1110.1(2), b = 2051.3(5), c = 2169.5(4) pm, α = 100.03(2)°, β = 103.404(15)°, γ = 97.63(2)°, R = 0.0480. [Cd(NPEt3)(O2C–CH3)]4 · 2 CH2Cl2: Space group C2/c, Z = 4, lattice dimensions at –80 °C: a = 1550.2(1), b = 2101.1(1), c = 1706.1(1) pm, β = 91.09(1)°, R = 0.0311.

[Co4(ν3-NPEt3)2(HNPEt3)2(O2C-CH3)2- (ν-OSiMe2OSiMe2O)2] - ein vierkerniger Cobalt(II)-Komplex mit Leiterstruktur / [Co4(ν3-NPEt3)2(HNPEt3)2(O2C-CH3)2-(ν-OSiMe2OSiMe2O)2] - a Tetranuclear Cobalt(II) Complex with Ladder Structure

The title compound has been prepared from cobalt( II) acetate and Me3SiNPEt3 in boiling toluene in the presence of silicon grease and traces of water as blue single crystals which were characterized by IR spectroscopy and by a crystal structure determination. Space group Pbca, Z = 8, lattice dimensions at -50 °C: a = 1449.3(1), b = 1724.9(1), c = 2356.6(2) pm, R = 0.0548. [Co4(ν3-NPEt3)2(HNPEt3)2(O2C-CH3)2-(v-OSiMe2OSiMe2O)2] has a centrosymmetric structure. The four cobalt atoms which are coordinated tetrahedrally are v3-bridged via the N atoms of the two (NPEt3-) groups and v2-bridged by the O atoms of the chelating (OSiMe2OSi-Me2O2-) units. The core atoms are arranged in three four-membered rings which are connected in a stair-like way.