16‐ and 18‐membered diphospha macrocycles (8, 12, and 15) have been synthesized from the corresponding 1,1′‐binaphthyl precursors (6, 11, and 14, resp.) and o‐phenylenebis(phenylphosphane) by means of high‐dilution conditions in 55, 49, and 87% yield. X‐ray structure analyses of 8a, 8b, 12b, and 12b · NiCl2 reveal their distinctly different conformations and conformational changes caused by complexation. These structural features are reflected in the pronounced different tendency of the compounds concerned to form Ni(II) and Pd(II) complexes.
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Widhalm et al. (1992) studied this question.
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