New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe2)3[N(TMS)NMe2] and Ta(NMe2)4[N(TMS)NMe2], and fluxional behavior of the amido and hydrazido ligands in solution

Shih Huang Huang; Tero Pilvi; Xiaoping Wang; Markku Leskelä; Michael G. Richmond

doi:10.1016/j.poly.2010.02.022

New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe₂)₃[N(TMS)NMe₂] and Ta(NMe₂)₄[N(TMS)NMe₂], and fluxional behavior of the amido and hydrazido ligands in solution

Shih Huang Huang, Tero Pilvi, Xiaoping Wang, Markku Leskelä, Michael G. Richmond

Single Crystal Diffraction

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Abstract

The synthesis and structural characterization of new tantalum(V) compounds containing a single hydrazido(I) ligand are reported. Hydrazinolysis of TaCl(NMe₂)₄ using trimethylsilyl(dimethyl)hydrazine affords the compound TaCl(NMe₂)₃[N(TMS)NMe₂] in essentially quantitative yield. Metathetical replacement of the chloride ligand in TaCl(NMe₂)₃[N(TMS)NMe₂] by LiNMe₂ gives the all-nitrogen coordinated compound Ta(NMe₂)₄[N(TMS)NMe₂]. VT ¹H NMR studies support the existence of low-energy pathways involving rotation about the Ta-N bonds of the ancillary amido and hydrazido ligands in both hydrazido-substituted compounds. X-ray crystallographic analyses confirm the octahedral disposition about the tantalum metal in TaCl(NMe₂)₃[N(TMS)NMe₂] and Ta(NMe₂)₄[N(TMS)NMe₂] and the presence of an η²-hydrazido(I) ligand. Preliminary data using Ta(NMe₂)₄[N(TMS)NMe₂] as an ALD precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented.

Original language	English
Pages (from-to)	1754-1759
Number of pages	6
Journal	Polyhedron
Volume	29
Issue number	7
DOIs	https://doi.org/10.1016/j.poly.2010.02.022
State	Published - May 10 2010

Funding

Financial support from the Robert A. Welch Foundation (Grant B-1093-MGR ) and LAM Semiconductor is greatly appreciated. X. Wang acknowledges the support by the U.S. Department of Energy, Office of Science , under Contract No. DE-AC05-00OR22725 managed by UT Battelle, LLC. We thank Prof. David M. Hoffman for providing us with a copy of the 1 H NMR spectrum of Ta(NMe 2 ) 5 and Dr. Yun Ling (UBC) for recording the EI mass spectra of TaCl(NMe 2 ) 3 [N(TMS)NMe 2 ] and Ta(NMe 2 ) 4 [N(TMS)NMe 2 ].

Funders	Funder number
Robert A. Welch Foundation	B-1093-MGR
U.S. Department of Energy
Office of Science

Keywords

ALD
Tantalum-amido compounds
Tantalum-hydrazido compounds
X-ray crystallography

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Huang, S. H., Pilvi, T., Wang, X., Leskelä, M., & Richmond, M. G. (2010). New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe₂)₃[N(TMS)NMe₂] and Ta(NMe₂)₄[N(TMS)NMe₂], and fluxional behavior of the amido and hydrazido ligands in solution. Polyhedron, 29(7), 1754-1759. https://doi.org/10.1016/j.poly.2010.02.022

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title = "New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe2)3[N(TMS)NMe2] and Ta(NMe2)4[N(TMS)NMe2], and fluxional behavior of the amido and hydrazido ligands in solution",

abstract = "The synthesis and structural characterization of new tantalum(V) compounds containing a single hydrazido(I) ligand are reported. Hydrazinolysis of TaCl(NMe2)4 using trimethylsilyl(dimethyl)hydrazine affords the compound TaCl(NMe2)3[N(TMS)NMe2] in essentially quantitative yield. Metathetical replacement of the chloride ligand in TaCl(NMe2)3[N(TMS)NMe2] by LiNMe2 gives the all-nitrogen coordinated compound Ta(NMe2)4[N(TMS)NMe2]. VT 1H NMR studies support the existence of low-energy pathways involving rotation about the Ta-N bonds of the ancillary amido and hydrazido ligands in both hydrazido-substituted compounds. X-ray crystallographic analyses confirm the octahedral disposition about the tantalum metal in TaCl(NMe2)3[N(TMS)NMe2] and Ta(NMe2)4[N(TMS)NMe2] and the presence of an η2-hydrazido(I) ligand. Preliminary data using Ta(NMe2)4[N(TMS)NMe2] as an ALD precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented.",

keywords = "ALD, Tantalum-amido compounds, Tantalum-hydrazido compounds, X-ray crystallography",

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Huang, SH, Pilvi, T, Wang, X, Leskelä, M & Richmond, MG 2010, 'New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe₂)₃[N(TMS)NMe₂] and Ta(NMe₂)₄[N(TMS)NMe₂], and fluxional behavior of the amido and hydrazido ligands in solution', Polyhedron, vol. 29, no. 7, pp. 1754-1759. https://doi.org/10.1016/j.poly.2010.02.022

New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe₂)₃[N(TMS)NMe₂] and Ta(NMe₂)₄[N(TMS)NMe₂], and fluxional behavior of the amido and hydrazido ligands in solution. / Huang, Shih Huang; Pilvi, Tero; Wang, Xiaoping et al.
In: Polyhedron, Vol. 29, No. 7, 10.05.2010, p. 1754-1759.

Research output: Contribution to journal › Article › peer-review

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AU - Huang, Shih Huang

AU - Pilvi, Tero

AU - Wang, Xiaoping

AU - Leskelä, Markku

AU - Richmond, Michael G.

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AB - The synthesis and structural characterization of new tantalum(V) compounds containing a single hydrazido(I) ligand are reported. Hydrazinolysis of TaCl(NMe2)4 using trimethylsilyl(dimethyl)hydrazine affords the compound TaCl(NMe2)3[N(TMS)NMe2] in essentially quantitative yield. Metathetical replacement of the chloride ligand in TaCl(NMe2)3[N(TMS)NMe2] by LiNMe2 gives the all-nitrogen coordinated compound Ta(NMe2)4[N(TMS)NMe2]. VT 1H NMR studies support the existence of low-energy pathways involving rotation about the Ta-N bonds of the ancillary amido and hydrazido ligands in both hydrazido-substituted compounds. X-ray crystallographic analyses confirm the octahedral disposition about the tantalum metal in TaCl(NMe2)3[N(TMS)NMe2] and Ta(NMe2)4[N(TMS)NMe2] and the presence of an η2-hydrazido(I) ligand. Preliminary data using Ta(NMe2)4[N(TMS)NMe2] as an ALD precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented.

KW - ALD

KW - Tantalum-amido compounds

KW - Tantalum-hydrazido compounds

KW - X-ray crystallography

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Huang SH, Pilvi T, Wang X, Leskelä M, Richmond MG. New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe₂)₃[N(TMS)NMe₂] and Ta(NMe₂)₄[N(TMS)NMe₂], and fluxional behavior of the amido and hydrazido ligands in solution. Polyhedron. 2010 May 10;29(7):1754-1759. doi: 10.1016/j.poly.2010.02.022