Phosphorane Iminato Complexes of Manganese and Cobalt with Heterocubane Structure

Abstract

Mn4N4 and Co4N4 cubes with almost square faces are found in the title compounds 1 and 2. They were obtained by the melt reaction of the anhydrous dihalides MnI2 and CoCl2, and Me3SiNPEt3. Complexes 1 and 2 are the first phosphorane iminato complexes of manganese(II) and cobalt(II) with heterocubane structure.

A μ3‐Alkoxo‐Bridged Tetranuclear [Cu4L2] Copper(II) Complex of a Hexadentate N2O4 Donor Ligand with a [6 + 0] Cu4O4 Cubane Core: Synthesis, Crystal Structure, and Magnetic Properties

“…Indeed, these small structural changes at the molecular scale usually have significant effects on their magnetic properties. [5] Quite generally, transition-metal complexes with a cubane-type structure (M 4 L n ) possess intramolecular hydroxo, alkoxo, azido, sulfido, or iminato bridges [6][7][8] and constitute a very interesting class of compounds. [9,10] Their originality is often found in their high-spin ground state that is induced, for example, by the pseudo-orthogonality of the magnetic orbitals of the metal ions.…”

Molecular cubes with high-spin ground states

“…Single molecule magnets need to have relatively high-spin ground states with an uniaxial magnetic anisotropy. Transition metal complexes with a cubane structure (M 4 L 4 ) are a very important class of compounds [10,11], where four metal ions are linked by Science hydroxo, alkoxo, azido, sulfido, or iminato bridges [12][13][14].…”

Phosphaniminato-Komplexe von Nickel(II) mit Heterocubanstruktur

“…Phosphaniminato-Komplexe zweiwertiger Ûbergangsmetalle vom Typ [MX(NPR 3 )] 4 mit Heterocubanstruktur und M 4 N 4 -Geru È st sind von Mangan [1,2], Kobalt [1,3], Nickel [2] und Zink [3,4] 4 [9] und die Kristallstrukturanalyse des Beispiels [NiCl(NPEt 3 )] 4 [2] beschra È nkt. Bei der Synthese des letzteren Derivats wurde bereits die bewa È hrte Methode der Thermolyse von silylierten Phosphaniminen mit Metallhalogeniden angewandt.…”

“…Da die dabei erzielten geringen Ausbeuten fu È r eine weitere Folgechemie der Halogeno±Nickel-Phosphaniminatokomplexe aber unvorteilhaft sind, haben wir die Synthese von Nickel-Phosphaniminatoheterocubanen mit den schwereren Homologen Brom und Iod ausgefu È hrt, woru È ber wir hier berichten. Im Gegensatz zu den hier beschriebenen Komplexen mit Koordinationszahl vier an den Nickelatomen haben die Ni-Atome in dem Azido-Heterocuban-Komplex [Ni(l 3 ±N 3 )(dbm)(EtOH)] 4 (dbmH = 1,3-Diphenylpropan-1,3-dion) [ [1,2], Co [3] und Zn [3,4], wa È hrend fu È r mNiX a È hnliche Frequenzlagen in den Spektren von Donor-Akzeptor-Komplexen [NiX 2 D 2 ] mit Koordinationszahl vier am Ni-Atom gefunden werden [11]. Vollsta È ndige IR-Spektren siehe Lit.…”