The reactions of bis(trimethylsilyl)ated forms of the Schiff base ligands N-(2-hydroxyphenyl)salicylideneamine {(HO)C(6)H(4)N(CH)C(6)H(4)(OH)}, N-(4-tert-butyl-2-hydroxyphenyl)salicylideneamine {(HO)((t)Bu)C(6)H(3)N(CH)C(6)H(4)(OH)}, N-(2-hydroxy-4-nitrophenyl)salicylideneamine {(HO)(O(2)N)C(6)H(3)N(CH)C(6)H(4)(OH)}, and the structurally related ligand 2,2'-azophenol with halogeno- and (trifluoromethyl)halogenophosphoranes yield a series of neutral hexacoordinate phosphorus(V) compounds by means of trimethylsilyl halide elimination. In all of these cases the ligands chelate in a meridional conformation in which bicyclic five- and six-membered chelate rings are formed through structures containing two phenolic P-O bonds and one N-P bond. The hexacoordinate nature of these compounds is evidenced by their high-field (31)P NMR chemical shifts and their characteristic J(PF) coupling patterns and is further substantiated by the crystal structures of {O((t)Bu)C(6)H(3)N(CH)C(6)H(4)O}PCl(3) and {OC(6)H(4)N=NC(6)H(4)O}PF(3). Crystal data for {O((t)Bu)C(6)H(3)N(CH)C(6)H(4)O}PCl(3): triclinic, space group P&onemacr; (No. 2), a = 11.167(1) Å, b = 15.684(1) Å, c = 17.047(2) Å, V = 2840(1) Å(3), Z = 2. Final R and R(w) values were 0.051 and 0.079, respectively. Crystal data for {OC(6)H(4)N=NC(6)H(4)O}PF(3): monoclinic, space group P2(1)/c (No. 14), a = 6.9393(8) Å, b = 12.450(2) Å, c = 13.907(2) Å, V = 1190.7(6) Å(3), Z = 4. Final R and R(w) values were 0.045 and 0.056, respectively. The molecular structures of {O((t)Bu)C(6)H(3)N(CH)C(6)H(4)O}PCl(3) and {OC(6)H(4)N=NC(6)H(4)O}PF(3) show that in both cases the Schiff base ligand chelates occupy the meridional plane about the six-coordinate phosphorus atom. In the case of {OC(6)H(4)N=NC(6)H(4)O}PF(3) the equivalent nitrogen atoms in the chelate rings are disordered to form half-occupancy pairs. The silylated form of the related thiobis(phenol), 2,2'-thiobis(4,6-tert-butylphenol), reacted similarly with pentavalent halides to form the six-coordinate complex [{2-O-3,5-((t)Bu)(2)C(6)H(2)}(2)S]PCl(3) which was also verified by a crystal structure. Crystal data for [{2-O-3,5-((t)Bu)(2)C(6)H(2)}(2)S]PCl(3): monoclinic P2(1)/n, a = 13.989(2), b = 13.594(2), c = 16.483(2) Å, beta = 97.98(2) degrees, V = 3104(2) Å(3), Z = 4; final R and R(w)() values were 0.039 and 0.052, respectively. In contrast to the above six coordinate complexes, this compound possesses a facial structure in which two phenoxy substituents form planar chelates centered on the bridging sulfur and intersecting at the P-S axis. The P-S bond length, 2.331(1) Å, is slightly shorter than has been previously observed in the example wherein the ligand possesses two tert-butyl groups and the phosphorus carries three OCH(2)CF(3 )substituents indicating stronger interaction between P and S in the present case.
