Phosphoraneiminato Complexes of Manganese and Cobalt with Heterocubane Structure

Abstract

The phosphoraneiminato complexes [MnBr(NPEt3)]4 (1) and [M4Br5{NP(NMe2)3}3] with M = Mn (2) and M = Co (3) are prepared by melting reactions from the anhydrous metal dibromides with the silylated phosphaneimines Me3SiNPR3 (R = Et, NMe2) in the presence of potassium fluoride. All complexes are characterized by crystal structure analyses. 1 forms an only slightly distorted Mn4N4 heterocubane skeleton with an approximate Td symmetry and short Mn…Mn distances of average 295.7 pm. In the structures of 2 and 3 one μ3‐NPEt3 ligand of 1 is replaced by one bromine atom with μ3‐function. This leads to the novel heterocubane type M4N3Br with approximate C3 symmetry. The deformation of the cubic skeleton leads to metal‐metal distances of different lengths, i. e. 292.7 and 323.6 pm in 2 and 274.4 and 306.2 pm in 3. Temperature dependent magnetic susceptibility measurements between 300 and 5 K on 1 have shown that strong antiferromagnetic coupling exists between the Mn(II) ions with S = 5/2, with a large negative Weiss constant of Θ = –694 K.

Multicomponent halide templating: The effect of structure-directing agents on the assembly of molecular and extended coordination compounds

“…The halide-capped triangle is particularly prominent in cubanetype systems [55][56][57][58][59][60]. These structures can be considered as being composed of four metal centres that adopt a tetrahedral arrangement, with each triangular face capped by a l 3 -X ligand (the metal ions and capping ligands combined then define the vertices of a cube).…”

“…These structures can be considered as being composed of four metal centres that adopt a tetrahedral arrangement, with each triangular face capped by a l 3 -X ligand (the metal ions and capping ligands combined then define the vertices of a cube). This can be achieved in an {M 4 X 4 } fashion [55][56][57], or in a {M 4 O 3 X} fashion [58][59][60]. In the late 80s and early 90s, {M 4 O 3 X} systems were heavily investigated in an attempt to elucidate the structure and reactivity of the active centre of photosystem II (PSII), a key component in photosynthesis [61][62][63][64][65][66].…”

Phosphaniminato- und Phosphanimin-Komplexe von Nickel(II). Die Kristallstrukturen von [Ni(O3SCF3)(NPMe3)]4, [Ni4Br5{NP(NMe2)3}3], [NiBr2{HNP(NMe2)3}2] und [Ni(PMePh2)4]

“…Die Struktur von 2 ist sehr a Èhnlich den Moleku È lstrukturen von [M 4 Br 5 {NP(NMe 2 ) 3 } 3 ] mit M = Mn und Co [5]. Der Ersatz eines N-Atoms des Heterokubans Ni 4 N 4 in 1 gegen ein Brom-Atom in 2 bedingt eine starke Verzerrung des Wu È rfelgeru È stes, das zwar ohne kristallographische Lagesymmetrie ist, aber entlang der topologischen Verbindungslinie Br(4)±Ni(4)±Br(5) eine anna Èhernd dreiza Èhlige Symmetrieachse erkennen la Èût (Abb.…”

“…Einen Zugang zu dem Nickel-Komplex [Ni 4 Br 5 -{NP(NMe 2 ) 3 } 3 ] (2) fanden wir in Anlehnung an die Synthesestrategie zur Herstellung der entsprechenden Komplexe von Mn II und Co II [5] in der Reaktion von Nickel(II)-bromid mit Me 3 SiNP(NMe 2 ) 3 in siedendem Toluol in Gegenwart von Natriumfluorid. 4 [18] durch Reaktion von CoCl 2 mit Me 3 SiNPMe 3 in siedendem Acetonitril in Gegenwart von Natriumfluorid und anschlieûender Rekristallisation aus Dichlormethan herstellen ko È nnen.…”

Experimental and computational studies on the solvent-controlled cluster isomerism of Ru3(H)(CO)9(NPPh3) and related dynamics

“…In fact, the R 3 PN unit is generally reported for a few polynuclear cubane-like compounds in which the N atom connects three non-bonded metal atoms. 5 Only in Fe 3 (NO)(CO) 7 (m-CO)(m 3 -NPPh 3 ), does the ligand cap a triangle of bonded metal atoms. 6 The reaction of Ru 3 (CO) 12 with an excess of Ph 3 PLNSiMe 3 under pyrolytic conditions (i.e.…”