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Synthesis and thermolytic behavior of mixed-valence homo- and heterometallic group 14 alkoxides

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic970618i· OSTI ID:642390
; ; ;  [1]
  1. Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry

The mixed-valence molecule Sn{sup II}Sn{sup IV} (OPr){sub 6} is conveniently synthesized and is shown to exchange bridging and terminal alkoxides in solution in its Sn({micro}-OPr){sub 3}Sn(OPr){sub 3} structure. Pb{sub 3}SnO(POr){sub 8} is synthesized and shown to undergo an intramolecular fluxional process in solution. Both molecules are sufficiently volatile for CVD study, and comparison of CVD behaviors of these and of M(OPr){sub 2} (M = Sn, Pb), Sn(POr){sub 4}, SnZr(OPr){sub 6}, and Pb{sub 3}-ZrO(OPr){sub 8} shows the reducing capacity of the isopropoxide moiety dominates the thermolytic behavior of all these species, giving metallic Sn or Pb in all cases. Only Zr, when it is present, forms ZrO{sub 2}. The oxide in Pb{sub 3}SnO(POr){sub 8}yields PbO (and 2 Pb{sup 0} and 1 Sn{sup 0}), in contrast to the relative electropositivity of Sn and Pb, a fact attributed to kinetic control of CVD behavior.

Sponsoring Organization:
USDOE, Washington, DC (United States)
OSTI ID:
642390
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 37; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English

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