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Intermolecular fluorine exchange in the systems SiF 4 –SiF 5  − , MeSiF 3 –MeSiF 4  − , PhSiF 3 –PhSiF 4  − , SiF 5  − –SiF 6  2− , SiF 4 –SiF 6  2− , and MeSiF 3 –SiF 6  2−  has been studied by fluorine and proton nmr spectroscopy. Exchange is postulated to involve fluorine-bridged intermediates; alternative pathways of exchange, such as fluoride dissociation or impurity (HF and H 2 O) catalyzed exchange, have been eliminated. Addition of NH 3  to SiF 5  − –SiF 6  2−  slows down exchange whereas addition of Et 2 NH to MeSiF 3  promotes exchange.

Fluorine exchange between four-, five-, and six-coordinate silicon compounds