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 ClSiMe3. 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 Ph2PCl and formation of chelate complexes LNi‐η5‐Cp and L2Pd 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.