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Inorganics 2018, 6(2), 47;

Unexpected Formation and Structural Characterization of a Dinuclear Sodium Half-Sandwich Complex

Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, 39106 Magdeburg, Germany
ETH Zürich, Laboratorium für Anorganische Chemie, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland
Author to whom correspondence should be addressed.
Received: 12 April 2018 / Revised: 4 May 2018 / Accepted: 7 May 2018 / Published: 9 May 2018
(This article belongs to the Special Issue Metallocene Complexes)
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Treatment of N,N′-diisopropylcarbodiimide with sodium cyclopentadienide (NaCp) in a molar ratio of 1:1 in THF solution resulted in formation of the unexpected dinuclear sodium half-sandwich complex [NaC5H3{C(NHiPr)(=NiPr)}2-1,2]2 (1) as colorless crystals in low yield. The newly formed ligand, which belongs to the group of 6-aminofulvene-2-aldiminate ligands, coordinates to sodium in an η5-coordination mode via the cyclopentadienyl ring. Dimerization occurs through additional chelating κN,N′-coordination of the amidine substituents. The NMR data of 1 indicated a slow dimer/monomer equilibrium in solution. A serendipitously isolated hydrolysis product, {µ-(iPrNH)2C=O}2[NaC5H3{C(NHiPr)(=NiPr)}2-1,2]2 (2), contains the new 6-aminofulvene-2-aldiminate ligand in the N,N′-chelating coordination mode with the cyclopentadiene ring being uncoordinated. In this case, dimerization occurs through the presence of two bridging neutral N,N′-diisopropylurea ligands. Both compounds have been structurally characterized by single-crystal X-ray diffraction. View Full-Text
Keywords: Sodium; amidinate ligand; cyclopentadienyl; aminofulvene-aldiminate; crystal structure Sodium; amidinate ligand; cyclopentadienyl; aminofulvene-aldiminate; crystal structure

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Harmgarth, N.; Liebing, P.; Hilfert, L.; Busse, S.; Edelmann, F.T. Unexpected Formation and Structural Characterization of a Dinuclear Sodium Half-Sandwich Complex. Inorganics 2018, 6, 47.

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