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Title: Evidence for carbon-sulfur bond cleavage in spontaneously adsorbed organosulfide-based monolayers at gold

Journal Article · · Journal of the American Chemical Society; (United States)
DOI:https://doi.org/10.1021/ja00104a071· OSTI ID:6617702
;  [1]
  1. Ames Lab.-USDOE, IA (United States) Iowa State Univ., Ames, IA (United States)

We have recently described several aspects of the electrode reactions of monolayers formed from alkanethiols and dialkyl disulfides at gold. This paper now discusses the findings and implications of two sets of electrochemical and surface characterization studies viz., X-ray photoelectron (XPS) and infrared reflection (IRS) spectroscopies. The first set of studies characterized monolayers formed at mica-supported Au(111) from dilute (0.1-1 mM) ethanolic solutions of butanethiol (BT) and butyl sulfide (BS/Au). The second set of experiments compared the monolayers formed from an asymmetric aryl sulfide, ethyl phenyl sulfide (PES), and a symmetric aryl sulfide, phenyl sulfide (PS), with those from thiophenol (TP) and ethanethiol (ET). The similarities in the E[sub p] and Q[sub d] values at TP/Au and PS/Au are consistent with the observations and subsequent interpretation of the electrochemical data at BT/Au and BS/Au. That is, the sulfur-gold interactions at TP/Au and PS/Au are effectively indistinguishable. Together, the above findings provide clear evidence for S-C cleavage in monolayers prepared at gold from organosulfides. 19 refs., 2 figs.

OSTI ID:
6617702
Journal Information:
Journal of the American Chemical Society; (United States), Vol. 116:25; ISSN 0002-7863
Country of Publication:
United States
Language:
English