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Title: Highly selective methyl transfer from methylsilanes to phenylthallium(III) crown ether complexes

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00025a007· OSTI ID:6395932

Reactions of (18-crown-6)phenylthallium(III) diperchlorate monohydrate (1a) with Me[sub 3]SiR (R = PhCH[sub 2], Et, Ph, CH[double bond]CH[sub 2], SiMe[sub 3], OSiMe[sub 3]) proceeded at 60[degrees]C to provide (18-crown-6)phenylmethylthallium(III) perchlorate (3) in good to excellent yields. Cleavage of the Me-Si bond in tetramethylsilane using 1a also occurred at 25[degrees]C, albeit for a long reaction time. The silicon-containing products of the reaction of 1a with benzyltrimethylsilane were siloxanes. Intramolecular trapping of the silyl fragments by a hydroxy group using (1,7-DTC)phenylthallium(III) bis(trifluoromethanesulfonate) (1b) was employed with trans-2-((trimethylsilyl)methyl)-1-cyclohexanol, affording a bicyclic silyl ether in 92% yield. 18 refs., 1 tab.

OSTI ID:
6395932
Journal Information:
Organometallics; (United States), Vol. 12:1; ISSN 0276-7333
Country of Publication:
United States
Language:
English