Syntheses, Structures, and Reactivity of 1‐Phosphanylnaphth‐2‐ols

P‐tertiary or amino‐substituted 1‐phosphanylnaphth‐2‐yl silyl ethers 3 are synthesized by stepwise reaction of lithium 1‐lithio‐2‐naphtholate 1 with chlorophosphanes and ClSiMe 3 . The free phosphanylnaphthols 4 are prepared by alcoholysis. As established by characteristic coupling constants and X‐ray structural analyses (of 3c, 4c ), 3 exhibit in solution and in the solid state a cis ‐bisecting conformation, whereas 4 prefers the opposite trans ‐bisecting arrangement, allowing easy protonation and formation of chelate complexes. Substitution reactions of phosphanylnaphtholates 2 with Ph 2 PCl and formation of chelate complexes LNi‐η 5 ‐Cp and L 2 Pd are described. Attempts to prepare secondary and primary phosphanylnaphthols failed because of facile cleavage of the P–C(naphthyl) bond in PH‐substituted 1‐phosphanylnaphth‐2‐ols.