| Abstract
| - The reaction of the [Ru(η5-C5H5)(η4-C5H4O)]+ fragment, anchored to self-assembled primer layers of NC5H4(CH2)2SiOx or NC(CH2)16SiOx on native silicon (Si/SiO2) substrates, with some tertiary phosphines PR3 has been studied by means of in situ ellipsometry and IR spectroscopy. The rate constants derived from in situ ellipsometry are found to be in surprisingly good agreement with those obtained in homogeneous solution for the reaction of [Ru(η5-C5H5)(η4-C5H4O)L]+ (L = pyridine, CH3CN) with PR3.
- The reaction of the [Ru(η5-C5H5)(η4-C5H4O)]+ fragment, anchored to self-assembled primerlayers of NC5H4(CH2)2SiOx or NC(CH2)16SiOx on native silicon (Si/SiO2) substrates, with sometertiary phosphines PR3 has been studied by means of in situ ellipsometry. In this way themetal center is effectively inaccessible, and the phosphine can attack only at the cyclopentadienone ligand site. The rate constants derived from in situ ellipsometry are found to bein surprisingly good agreement with those obtained in homogeneous solution for the reactionof [Ru(η5-C5H5)(η4-C5H4O)L]+ (L = pyridine, CH3CN) with PR3 to yield the η3-cyclopentenoylcomplexes [Ru(η5-C5H5)(η3-C5H4O-2-PR3)L]+. The nature of the ruthenium complexes at thesurface has been established by IR spectroscopy in combination with XPS measurements.Thus, the present study provides a rare example of a direct comparison of the same intrinsicreaction occurring in homogeneous solution and at the solid−liquid interface.
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