Synthesis and structures of novel bis- and tetrakis-cyclodiphosphazane compounds appended to a diol or a tetra-ol

Abstract

The bis-cyclodiphosphazane compound Et₂C[CH₂OP(μ-N-t-Bu)₂PNH-t-Bu]₂ (2) and the tetrakis-cyclodiphosphazane compound C[CH₂OP(μ-N-t-Bu)₂PNH-t-Bu]₄ (3) have been synthesized by treating 2,2-diethyl-1,3-propanediol or pentaerythritol with 2 or 4 equiv. of [ClP(μ-N-t-Bu)₂P(HN-t-Bu)] (1), respectively. Compounds 2 and 3 have been characterized by X-ray crystallography and solution state NMR. Oxidative addition of o-chloranil to 2 and 3 yields the novel compounds Et₂C[CH₂OP(μ -N-t-Bu)₂P{(HN-t-Bu)(1,2-O₂C₆Cl₄)}]₂ (4) and C[CH₂OP(μ-N-t-Bu)₂P{(HN-t-Bu)(1,2-O₂C₆Cl₄)}]₄ (5) having two or four P(III)---N---P(V) centers, respectively. The ³¹P NMR spectra of compounds 4 and 5 show characteristic doublets in the tri- and penta-coordinated regions.