Reductive elimination of hypersilyl halides from zinc (II) complexes. Implications for electropositive metal thin film growth

Sirimanne, Chatu T.; Kerrigan, Marissa M.; Martin, Philip D.; Kanjolia, Ravindra K.; Elliott, Simon D.; Winter, Charles H.

Reductive elimination of hypersilyl halides from zinc (II) complexes. Implications for electropositive metal thin film growth

Files

Sirimanne_Elliott_Winter_InorgChem_54_7_2015_submitted.pdf(296.54 KB)

Date

2015-01-05

Authors

Sirimanne, Chatu T.

Kerrigan, Marissa M.

Martin, Philip D.

Kanjolia, Ravindra K.

Elliott, Simon D.

Winter, Charles H.

Publisher

American Chemical Society

Published Version

10.1021/ic502184f

Abstract

Treatment of Zn(Si(SiMe3)3)2 with ZnX2 (X = Cl, Br, I) in tetrahydrofuran (THF) at 23 °C afforded [Zn(Si(SiMe3)3)X(THF)]2 in 83–99% yield. X-ray crystal structures revealed dimeric structures with Zn2X2 cores. Thermogravimetric analyses of [Zn(Si(SiMe3)3)X(THF)]2 demonstrated a loss of coordinated THF between 50 and 155 °C and then single-step weight losses between 200 and 275 °C. The nonvolatile residue was zinc metal in all cases. Bulk thermolyses of [Zn(Si(SiMe3)3)X(THF)]2 between 210 and 250 °C afforded zinc metal in 97–99% yield, Si(SiMe3)3X in 91–94% yield, and THF in 81–98% yield. Density functional theory calculations confirmed that zinc formation becomes energetically favorable upon THF loss. Similar reactions are likely to be general for M(SiR3)n/MXn pairs and may lead to new metal-film-growth processes for chemical vapor deposition and atomic layer deposition.

Keywords

Chemical vapor deposition , Atomic layer deposition (ALD)

Citation

SIRIMANNE, C. T., KERRIGAN, M. M., MARTIN, P. D., KANJOLIA, R. K., ELLIOTT, S. D. & WINTER, C. H. 2015. Reductive Elimination of Hypersilyl Halides from Zinc(II) Complexes. Implications for Electropositive Metal Thin Film Growth. Inorganic Chemistry, 54, 7-9. http://dx.doi.org/10.1021/ic502184f