Molecules that Turn Themselves Inside-Out: Tuning in/out Equilibria and Homeomorphic Isomerization in Macrobicyclic Dibridgehead Diphosphines P((CH2 )n )3 P Newly Accessible by Earth-Abundant-Metal Templates.
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abstract
Photolyses of trans-Fe(CO)3 (P((CH2 )n )3 P) (n=10 (a), 12 (b), 14 (c), 16 (d), 18 (e)) in the presence of PMe3 provide the first economical and scalable route to macrobicyclic dibridgehead diphosphines P((CH2 )n )3 P (1). These are isolated as mixtures of in,in/out,out isomers that equilibrate with degenerate in,out/out,in isomers at 150C via pyramidal inversion at phosphorus. For the entire series, VT 31 P NMR data establish or bound Keq , rates, and activation parameters for a variety of phenomena, many of which involve homeomorphic isomerizations, topological processes by which certain molecules can turn themselves inside out (e.g., in,inout,out). This provides the first detailed mapping of such trends in homologous series of aliphatic bicyclic compounds XE((CH2 )n )3 EX with any type of bridgehead. Isomeric diborane adducts 1a,d2BH3 are also characterized. Crystal structures of out,out-1a and in,in-1a2BH3 aid isomer assignments and reveal unusual cage conformations.
