ISSN:
0044-2313
Keywords:
Phosphoraneiminato Complexes of Manganese and Nickel
;
Syntheses
;
Crystal Structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Phosphoraneiminato Complexes of Manganese(II) and Nickel(II) with Heterocubane Structure. Crystal Structures of [MCl(NPEt3)]4 with M = Mn and NiThe phosphoraneiminato complexes [MCl(NPEt3)]4 with M = manganese and nickel as well as [MnBr(NPEt3)]4 are formed from the anhydrous halides MX2 and excess phosphoraneimine Me3SiNPEt3 by fusion reaction. They form paramagnetic, moisture-sensitive, orange (M = Mn) and turquoisegreen (M = Ni) crystals, respectively, which are characterized by i.r. spectroscopy and by crystal structure determinations.[MnCl(NPEt3)]4 (1): Space group C2/c, Z = 4, structure solution with 3 591 unique reflections, (2 811 〉 2σ(I)) R = 0.036. Lattice dimensions at -50°C: a = 2104.3, b = 1100.6, c = 1966.5 pm, β = 115.87°.[NiCl(NPEt3)]4 (2): Space group C2/c, Z = 4, structure solution with 2 711 unique reflections, (1611 〉 2σ(I)) R = 0.056. Lattice dimensions at -50°C: a = 2051.6, b = 1099.2, c = 1954.6 pm, β = 115.80°.1 and 2 are isostructural with one another. They form heterocubane structures in which the metal atoms are linked via μ3-N-bridges of the phosphoraneiminato groups with M4N4 bridge-type bond angles close to 90°.
Notes:
Die Phosphaniminato-Komplexe [MCl(NPEt3)]4 mit M = Mangan und Nickel sowie [MnBr(NPEt3)]4 entstehen durch Schmelzreaktion aus den wasserfreien Halogeniden MX2 und überschüssigem Phosphanimin Me3SiNPEt3. Sie bilden paramagnetische, feuchtigkeitsempfindliche, orange (M = Mn) bzw. türkisgrüne (M = Ni) Kristalle, die wir IR-spektroskopisch und durch Kristallstrukturanalysen charakterisiert haben. [MnCl(NPEt3)]4 (1): Raumgruppe C2/c, Z = 4, Strukturlösung mit 3 591 unabhängigen Reflexen, (2811 〉 2σ(I)) R = 0,036. Gitterkonstanten bei -50°C: a = 2104,3; b = 1100,6; c = 1966,5 pm, β = 115,87°.[NiCl(NPEt3)]4 (2): Raumgruppe C2/c, Z = 4, Strukturlösung mit 2 771 unabhängigen Reflexen, (1 611 〉 2σ(I)) R = 0,056. Gitterkonstanten bei -50°C: a = 2051,6; b = 1 099,2; c = 1954,6 pm, β = 115,80°.1 und 2 sind miteinander isotyp. Sie bilden Heterocuban-Strukturen, in denen die Metallatome über μ3-N-Brücken der Phosphaniminato-Gruppen verknüpft sind mit M4N4-Brückenbindungswinkeln nahe bei 90°.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19956211122
