Reactions of tetrakis(dimethylamide)-titanium, -zirconium and -hafnium with silanes

Synthesis of unusual amide hydride complexes and mechanistic studies of titanium-silicon-nitride (Ti-Si-N) formation

X. Liu, Y. D. Wu, H. Cai, Y. Yang, T. Chen, C. E. Vallet, R. A. Zuhr, D. B. Beach, Z. H. Peng, Zhongzhi Wu, T. E. Concolino, A. L. Rheingold, Z. Xue

Research output: Contribution to journalArticle

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Abstract

M(NMe2)4 (M = Ti, Zr, Hf) were found to react with H2SiR′Ph (R′ = H, Me, Ph) to yield H2, aminosilanes, and black solids. Unusual amide hydride complexes [(Me2N)3M(μ-H) (μ-NMe2)2]2M (M = Zr, 1; Hf, 2) were observed to be intermediates and characterized by single-crystal X-ray diffraction. [(Me2N)3M(μ-D) (μ-NMe2)2]2M (1-d2, 2-d2) were prepared through reactions of M(NMe2)4 with D2SiPh2. Reactions of (Me2N)3ZrSi(SiMe3)3 (5) with H2SiR′Ph were found to give aminosilanes and (Me2N)2Zr(H)Si(SiMe3)3 (6). These reactions are reversible through unusual equilibria such as (Me2N)3ZrSi(SiMe3)3 (5) + H2SiPh2 ⇄ (Me2N)2Zr(H)Si(SiMe3)3 (6) + HSi(NMe2)Ph2. The deuteride ligand in (Me2N)2Zr(D)Si(SiMe3)3 (6-d1) undergoes H-D exchange with H2SiR′Ph (R′ = Me, H) to give 6 and HDSiR′Ph. The reaction of Ti(NMe2)4 with SiH4 in chemical vapor deposition at 450 °C yielded thin Ti-Si-N ternary films containing TiN and Si3N4. Ti(NMe2)4 reacts with SiH4 at 23 °C to give H2, HSi(NMe2)3, and a black solid. HNMe2 was not detected in this reaction. The reaction mixture, upon heating, gave TiN and Si3N4 powders. Analyses and reactivities of the black solid revealed that it contained -H and unreacted -NMe2 ligands but no silicon-containing ligand. Ab initio quantum chemical calculations of the reactions of Ti(NR2)4 (R = Me, H) with SiH4 indicated that the formation of aminosilanes and HTi(NR2)3 was favored. These calculations also showed that HTi(NH2)3 (3b) reacted with SiH4 or H3Si-NH2 in the following step to give H2Ti(NH2)2 (4b) and aminosilanes. The results in the current studies indicated that the role of SiH4 in its reaction with Ti(NMe2)4 was mainly to remove amide ligands as HSi(NMe2)3. The removal of amide ligands is incomplete, and the reaction thus yielded "=Ti(H)(NMe2)" as the black solid. Subsequent heating of the black solid and HSi-(NMe2)3 may then yield TiN and Si3N4, respectively, as the Ti-Si-N materials.

Original languageEnglish (US)
Pages (from-to)8011-8021
Number of pages11
JournalJournal of the American Chemical Society
Volume123
Issue number33
DOIs
StatePublished - Oct 8 2001

Fingerprint

Hafnium
Silanes
Titanium nitride
Titanium
Silicon nitride
Amides
Zirconium
Hydrides
Ligands
Heating
Silicon
X-Ray Diffraction
Powders
Chemical vapor deposition
silicon nitride
titanium nitride
Single crystals
X ray diffraction
Hydrogen

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Reactions of tetrakis(dimethylamide)-titanium, -zirconium and -hafnium with silanes : Synthesis of unusual amide hydride complexes and mechanistic studies of titanium-silicon-nitride (Ti-Si-N) formation. / Liu, X.; Wu, Y. D.; Cai, H.; Yang, Y.; Chen, T.; Vallet, C. E.; Zuhr, R. A.; Beach, D. B.; Peng, Z. H.; Wu, Zhongzhi; Concolino, T. E.; Rheingold, A. L.; Xue, Z.

In: Journal of the American Chemical Society, Vol. 123, No. 33, 08.10.2001, p. 8011-8021.

Research output: Contribution to journalArticle

Liu, X. ; Wu, Y. D. ; Cai, H. ; Yang, Y. ; Chen, T. ; Vallet, C. E. ; Zuhr, R. A. ; Beach, D. B. ; Peng, Z. H. ; Wu, Zhongzhi ; Concolino, T. E. ; Rheingold, A. L. ; Xue, Z. / Reactions of tetrakis(dimethylamide)-titanium, -zirconium and -hafnium with silanes : Synthesis of unusual amide hydride complexes and mechanistic studies of titanium-silicon-nitride (Ti-Si-N) formation. In: Journal of the American Chemical Society. 2001 ; Vol. 123, No. 33. pp. 8011-8021.
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title = "Reactions of tetrakis(dimethylamide)-titanium, -zirconium and -hafnium with silanes: Synthesis of unusual amide hydride complexes and mechanistic studies of titanium-silicon-nitride (Ti-Si-N) formation",
abstract = "M(NMe2)4 (M = Ti, Zr, Hf) were found to react with H2SiR′Ph (R′ = H, Me, Ph) to yield H2, aminosilanes, and black solids. Unusual amide hydride complexes [(Me2N)3M(μ-H) (μ-NMe2)2]2M (M = Zr, 1; Hf, 2) were observed to be intermediates and characterized by single-crystal X-ray diffraction. [(Me2N)3M(μ-D) (μ-NMe2)2]2M (1-d2, 2-d2) were prepared through reactions of M(NMe2)4 with D2SiPh2. Reactions of (Me2N)3ZrSi(SiMe3)3 (5) with H2SiR′Ph were found to give aminosilanes and (Me2N)2Zr(H)Si(SiMe3)3 (6). These reactions are reversible through unusual equilibria such as (Me2N)3ZrSi(SiMe3)3 (5) + H2SiPh2 ⇄ (Me2N)2Zr(H)Si(SiMe3)3 (6) + HSi(NMe2)Ph2. The deuteride ligand in (Me2N)2Zr(D)Si(SiMe3)3 (6-d1) undergoes H-D exchange with H2SiR′Ph (R′ = Me, H) to give 6 and HDSiR′Ph. The reaction of Ti(NMe2)4 with SiH4 in chemical vapor deposition at 450 °C yielded thin Ti-Si-N ternary films containing TiN and Si3N4. Ti(NMe2)4 reacts with SiH4 at 23 °C to give H2, HSi(NMe2)3, and a black solid. HNMe2 was not detected in this reaction. The reaction mixture, upon heating, gave TiN and Si3N4 powders. Analyses and reactivities of the black solid revealed that it contained -H and unreacted -NMe2 ligands but no silicon-containing ligand. Ab initio quantum chemical calculations of the reactions of Ti(NR2)4 (R = Me, H) with SiH4 indicated that the formation of aminosilanes and HTi(NR2)3 was favored. These calculations also showed that HTi(NH2)3 (3b) reacted with SiH4 or H3Si-NH2 in the following step to give H2Ti(NH2)2 (4b) and aminosilanes. The results in the current studies indicated that the role of SiH4 in its reaction with Ti(NMe2)4 was mainly to remove amide ligands as HSi(NMe2)3. The removal of amide ligands is incomplete, and the reaction thus yielded {"}=Ti(H)(NMe2){"} as the black solid. Subsequent heating of the black solid and HSi-(NMe2)3 may then yield TiN and Si3N4, respectively, as the Ti-Si-N materials.",
author = "X. Liu and Wu, {Y. D.} and H. Cai and Y. Yang and T. Chen and Vallet, {C. E.} and Zuhr, {R. A.} and Beach, {D. B.} and Peng, {Z. H.} and Zhongzhi Wu and Concolino, {T. E.} and Rheingold, {A. L.} and Z. Xue",
year = "2001",
month = "10",
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TY - JOUR

T1 - Reactions of tetrakis(dimethylamide)-titanium, -zirconium and -hafnium with silanes

T2 - Synthesis of unusual amide hydride complexes and mechanistic studies of titanium-silicon-nitride (Ti-Si-N) formation

AU - Liu, X.

AU - Wu, Y. D.

AU - Cai, H.

AU - Yang, Y.

AU - Chen, T.

AU - Vallet, C. E.

AU - Zuhr, R. A.

AU - Beach, D. B.

AU - Peng, Z. H.

AU - Wu, Zhongzhi

AU - Concolino, T. E.

AU - Rheingold, A. L.

AU - Xue, Z.

PY - 2001/10/8

Y1 - 2001/10/8

N2 - M(NMe2)4 (M = Ti, Zr, Hf) were found to react with H2SiR′Ph (R′ = H, Me, Ph) to yield H2, aminosilanes, and black solids. Unusual amide hydride complexes [(Me2N)3M(μ-H) (μ-NMe2)2]2M (M = Zr, 1; Hf, 2) were observed to be intermediates and characterized by single-crystal X-ray diffraction. [(Me2N)3M(μ-D) (μ-NMe2)2]2M (1-d2, 2-d2) were prepared through reactions of M(NMe2)4 with D2SiPh2. Reactions of (Me2N)3ZrSi(SiMe3)3 (5) with H2SiR′Ph were found to give aminosilanes and (Me2N)2Zr(H)Si(SiMe3)3 (6). These reactions are reversible through unusual equilibria such as (Me2N)3ZrSi(SiMe3)3 (5) + H2SiPh2 ⇄ (Me2N)2Zr(H)Si(SiMe3)3 (6) + HSi(NMe2)Ph2. The deuteride ligand in (Me2N)2Zr(D)Si(SiMe3)3 (6-d1) undergoes H-D exchange with H2SiR′Ph (R′ = Me, H) to give 6 and HDSiR′Ph. The reaction of Ti(NMe2)4 with SiH4 in chemical vapor deposition at 450 °C yielded thin Ti-Si-N ternary films containing TiN and Si3N4. Ti(NMe2)4 reacts with SiH4 at 23 °C to give H2, HSi(NMe2)3, and a black solid. HNMe2 was not detected in this reaction. The reaction mixture, upon heating, gave TiN and Si3N4 powders. Analyses and reactivities of the black solid revealed that it contained -H and unreacted -NMe2 ligands but no silicon-containing ligand. Ab initio quantum chemical calculations of the reactions of Ti(NR2)4 (R = Me, H) with SiH4 indicated that the formation of aminosilanes and HTi(NR2)3 was favored. These calculations also showed that HTi(NH2)3 (3b) reacted with SiH4 or H3Si-NH2 in the following step to give H2Ti(NH2)2 (4b) and aminosilanes. The results in the current studies indicated that the role of SiH4 in its reaction with Ti(NMe2)4 was mainly to remove amide ligands as HSi(NMe2)3. The removal of amide ligands is incomplete, and the reaction thus yielded "=Ti(H)(NMe2)" as the black solid. Subsequent heating of the black solid and HSi-(NMe2)3 may then yield TiN and Si3N4, respectively, as the Ti-Si-N materials.

AB - M(NMe2)4 (M = Ti, Zr, Hf) were found to react with H2SiR′Ph (R′ = H, Me, Ph) to yield H2, aminosilanes, and black solids. Unusual amide hydride complexes [(Me2N)3M(μ-H) (μ-NMe2)2]2M (M = Zr, 1; Hf, 2) were observed to be intermediates and characterized by single-crystal X-ray diffraction. [(Me2N)3M(μ-D) (μ-NMe2)2]2M (1-d2, 2-d2) were prepared through reactions of M(NMe2)4 with D2SiPh2. Reactions of (Me2N)3ZrSi(SiMe3)3 (5) with H2SiR′Ph were found to give aminosilanes and (Me2N)2Zr(H)Si(SiMe3)3 (6). These reactions are reversible through unusual equilibria such as (Me2N)3ZrSi(SiMe3)3 (5) + H2SiPh2 ⇄ (Me2N)2Zr(H)Si(SiMe3)3 (6) + HSi(NMe2)Ph2. The deuteride ligand in (Me2N)2Zr(D)Si(SiMe3)3 (6-d1) undergoes H-D exchange with H2SiR′Ph (R′ = Me, H) to give 6 and HDSiR′Ph. The reaction of Ti(NMe2)4 with SiH4 in chemical vapor deposition at 450 °C yielded thin Ti-Si-N ternary films containing TiN and Si3N4. Ti(NMe2)4 reacts with SiH4 at 23 °C to give H2, HSi(NMe2)3, and a black solid. HNMe2 was not detected in this reaction. The reaction mixture, upon heating, gave TiN and Si3N4 powders. Analyses and reactivities of the black solid revealed that it contained -H and unreacted -NMe2 ligands but no silicon-containing ligand. Ab initio quantum chemical calculations of the reactions of Ti(NR2)4 (R = Me, H) with SiH4 indicated that the formation of aminosilanes and HTi(NR2)3 was favored. These calculations also showed that HTi(NH2)3 (3b) reacted with SiH4 or H3Si-NH2 in the following step to give H2Ti(NH2)2 (4b) and aminosilanes. The results in the current studies indicated that the role of SiH4 in its reaction with Ti(NMe2)4 was mainly to remove amide ligands as HSi(NMe2)3. The removal of amide ligands is incomplete, and the reaction thus yielded "=Ti(H)(NMe2)" as the black solid. Subsequent heating of the black solid and HSi-(NMe2)3 may then yield TiN and Si3N4, respectively, as the Ti-Si-N materials.

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