title: Reductive elimination of hypersilyl halides from zinc(II) complexes. Implications for electropositive metal thin film growth.
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.
authors.affiliation: Department of Chemistry, Wayne State University , Detroit, Michigan 48202, United States.
authors.forename: Chatu T
authors.initials: CT
authors.lastname: Sirimanne
authors.forename: Marissa M
authors.initials: MM
authors.lastname: Kerrigan
authors.forename: Philip D
authors.initials: PD
authors.lastname: Martin
authors.forename: Ravindra K
authors.initials: RK
authors.lastname: Kanjolia
authors.forename: Simon D
authors.initials: SD
authors.lastname: Elliott
authors.forename: Charles H
authors.initials: CH
authors.lastname: Winter