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Synthesis and Structural Characterization of the Pentanuclear Tantalum Cluster Ta5(μ5-N)(μ3-NiPr)2(μ2-NiPr)6(η1-NiPr)4(η1-NHiPr)2 from the Reaction of Ta(NMe2)5 and iPrNH2: Unprecedented Formation of a Hinged-Butterfly Cluster Containing an Interstitial Nitride, Imido Groups, and Amido Groups

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Abstract

The reaction of Ta(NMe2)5 with excess iPrNH2 (20-25 equivalents) at room temperature yields the pentanuclear tantalum cluster Ta5(μ5-N)(μ3-NiPr)2(μ2-NiPr)6(η1-NiPr)4(η1-NHiPr)2 (1) in 17 % yield. 1 has been characterized by 1H NMR spectroscopy and X-ray diffraction analysis. 1·pentane crystallizes in the monoclinic space group P2(1)/c, a = 21.669(2) Å, b = 12.6412(9) Å, c = 43.451(3) Å, β = 91.535(1)°, V = 11898(2) Å3, Z = 4, and dcalc = 1.961 Mg/m3; R = 0.0723, R w = 0.1599 for 24154 reflections with I > 2σ(I). The structural highlights in 1 include a hinged-butterfly arrangement of tantalum atoms that encapsulate an interstitial μ5-nitride moiety, three different types of imido groups, and one set of amido ligands. Compound 1 represents the first structurally characterized paradigm of a polynuclear cluster whose coordination sphere contains five different types of nitrogen ligands.

Graphical Abstract

The homoleptic amido compound Ta(NMe2)5 reacts with a large excess of iPrNH2 at room temperature to furnish the pentanuclear tantalum cluster Ta5(μ5-N)(μ3-NiPr)2(μ2-NiPr)6(η1-NiPr)4(η1-NHiPr)2 (1) in 17 % yield. The presence of an interstitial nitride moiety, three different types of imido groups, and one set of amido ligands in cluster 1 has been established by X-ray crystallography.

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Acknowledgments

Financial support from the Robert A. Welch Foundation (Grant B-1093-MGR) and Lam Semiconductor is much appreciated. NSF support of the UNT NMR facility through grant CHE-0840518 is acknowledged.

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  1. Department of Chemistry, University of North Texas, Denton, TX, 76203, USA

    Shih-Huang Huang, Vladimir N. Nesterov & Michael G. Richmond

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  1. Shih-Huang Huang
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  2. Vladimir N. Nesterov
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  3. Michael G. Richmond
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Correspondence to Michael G. Richmond.

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Huang, SH., Nesterov, V.N. & Richmond, M.G. Synthesis and Structural Characterization of the Pentanuclear Tantalum Cluster Ta5(μ5-N)(μ3-NiPr)2(μ2-NiPr)6(η1-NiPr)4(η1-NHiPr)2 from the Reaction of Ta(NMe2)5 and iPrNH2: Unprecedented Formation of a Hinged-Butterfly Cluster Containing an Interstitial Nitride, Imido Groups, and Amido Groups. J Chem Crystallogr 42, 916–922 (2012). https://doi.org/10.1007/s10870-012-0336-3

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