An unusual (10,3)-a racemic twofold interpenetrating network assembled from isolable tris(cyclopentadienyl)manganate and cesocene building blocks.
The syntheses and X-ray crystal structures of [([18]crown-6)2Cs](+)-[Cp3Mn]- (1), [([18]crown-6)2Cs](+)-[Cp'3Mn]- (2), [CsCp'] (3), [(CsCp')2-([18]crown-6)] (4), and Cs[MnCp3] (5), and the synthesis of Cs[MnCp'3] (6) are reported (Cp' = C5H4Me). The anions [Cp3Mn]- (1-) and [Cp'3Mn]- (2-) are characterized by eta 2 coordination of all three Cp or Cp' rings. Measurements of the magnetic susceptibilities chi M resulted in values of mu eff = 6.20 microB (300 K), mu eff = 6.33 microB (301 K), and mu eff = 5.83 microB (300 K) for 1, 2, and 5, respectively, which are indicative of high-spin d5-Mn2+ centers. Density functional calculations illustrate that the coordination mode of 1- is characteristic for its sextet electronic ground state. Compound 3 forms infinite chains of cesocene-type sandwiches in the solid state, which are broken up into small subunits by the addition of crown ether to form 4. Compound 5 is a rare example of a (10,3)-a racemic interpenetrating network that crystallizes in the orthorhombic space group Pbca.
Anorganisch-Chemisches Institut der Universität Zürich Winterthurerstrasse 190, 8057 Zürich, Switzerland.
Sohrab
S
Kheradmandan
Helmut W
HW
Schmalle
Heiko
H
Jacobsen
Olivier
O
Blacque
Thomas
T
Fox
Heinz
H
Berke
Mathias
M
Gross
Silvio
S
Decurtins
D003460:Crystallization; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008280:Magnetics; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
D009942:Organometallic Compounds; C013108:metallocene; C044679:manganese cyclopentadienyl tricarbonyl