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-naphtholat e 1 with chlorophosphanes and ClSiMe(3). The free phosphanylnaphthols 4 are prepared alcoholysis. As established by characteristic coupling constants and X-ray structural analyses (of 3c, 4c), 3 exhibit in solu tion and in the solid state a cis-bisecting conformation, whereas 4 pr efers the opposite trans-bisecting arrangement, allowing easy protonat ion and formation of chelate complexes. Substitution reactions of phos phanylnaphtholates 2 with Ph(2)PCl and formation of chelate complexes LNi-eta(5)-Cp and L(2)Pd are described. Attempts to prepare secondary and primary phosphanylnaphthols failed because of facile cleavage of t he P-C(naphthyl) bond in PH-substituted 1-phosphanylnaphth-2-ols.