Abstract
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.
Highlights
[R2 NC(NR0 )2 ]− (Scheme 1)—have become indispensable in various fields of organometallic and coordination chemistry [1,2,3,4,5,6,7,8,9]
Alkyl-substituted amidinate and guanidinate complexes of various metals have been established as ALD and MOCVD precursors for the deposition of thin films of useful materials, such as metals, metal oxides or metal nitrides, among others [17,18,19]
5 -cyclopentadienyl ring of one of the ligands and to both N donor atoms centers is ligated both to the η complex 1, the ligand system in 1 is rather unusual, as it bears additional secondary amino of the other
Summary
N,N 0 -Chelating anionic ligands—such as the amidinates, [RC(NR0 )2 ]− , and guanidinates,. [R2 NC(NR0 )2 ]− (Scheme 1)—have become indispensable in various fields of organometallic and coordination chemistry [1,2,3,4,5,6,7,8,9] These ligands form well-defined complexes with virtually every metallic element in the periodic system. A generally applicable synthetic route to lithium three the N–C–N backbone be varied. R′ can be varied in a in wide rangerange and, a large library of amidinate ligands has become available [1,2,3,4,5,6,7,8,9]. A large library of of amidinate ligands guanidinate anions can be accessed in a manner by adding lithium diorganoamides, LiNR2, guanidinate anions can be accessed in a manner by adding lithium diorganoamides, LiNR22, to carbodiimides.
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