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Chem."],"accepted":{"date-parts":[[2015,2,11]]},"abstract":"<jats:p>Two chlorophosphites, the biphenyl-based BIFOP\u2013Cl and the diphenyl ether-based O\u2013BIFOP\u2013Cl, exhibit striking differences regarding their reaction with water. While BIFOP\u2013Cl is nearly completely unreactive, its oxo-derivative O\u2013BIFOP\u2013Cl reacts instantly with water, yielding a tricyclic hydrocarbon unit after rearrangement. The analysis of the crystal structure of O\u2013BIFOP\u2013Cl and BIFOP\u2013Cl revealed that the large steric demand of encapsulating fenchane units renders the phosphorus atom nearly inaccessible by nucleophilic reagents, but only for BIFOP\u2013Cl. In addition to the steric effect, a hypervalent P(III)\u2013O interaction as well as an electronic conjugation effect causes the high reactivity of O\u2013BIFOP\u2013Cl. A DFT study of the hydrolysis in BIFOP\u2013Cl verifies a higher repulsive interaction to water and a decreased leaving tendency of the chloride nucleofuge, which is caused by the fenchane units. This high stability of BIFOP\u2013Cl against nucleophiles supports its application as a chiral ligand, for example, in Pd catalysts.<\/jats:p>","DOI":"10.3762\/bjoc.11.36","type":"journal-article","created":{"date-parts":[[2015,3,4]],"date-time":"2015-03-04T10:14:53Z","timestamp":1425464093000},"page":"313-322","source":"Crossref","is-referenced-by-count":3,"title":["An unusually stable chlorophosphite: What makes BIFOP\u2013Cl so robust against hydrolysis?"],"prefix":"10.3762","volume":"11","author":[{"given":"Roberto","family":"Blanco Trillo","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"J\u00f6rg 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