Single-Point Remote Control of Flapping Motion in Clothespin-Shaped Bimetallic Palladium Complexes Based on the N(sp(2))-N(sp(3)) Interconversion in Amide Functionalities.

Abstract

The synthesis, structure, and flapping motion of clothespin-shaped binuclear trans-bis(salicylaldiminato)palladium(II) complexes (anti-1) with 4-azaheptamethylene linkers bearing amide (a-g), urethane (h), or urea (i) functionalities are described in this report. Various 2D (1)H NMR experiments and XRD analyses indicate that the amide- and urethane-linked anti-1 a,b,d-h complexes exist as equilibrated mixtures of major and minor conformers I and II in CDCl3, whereas the complexes anti-1 c and i were observed as a single species. The mapping of NOESY cross-peaks between conformers I and II revealed that the equilibration of the major and minor conformers of anti-1 a,b,d-h proceeds by two pathways, namely a nonrotatory flapping motion of the coordinated blades and a nonflapping rotation of C-N bonds, whereas the equilibration of anti-1 c proceeds by simultaneous flapping and rotation motions. Kinetic studies carried out by means of (1)H-(1)H EXSY experiments revealed that 1) the ΔG(≠) 298K values for the flapping motion are controlled remotely by the steric and electronic effects of the RCON functionalities and 2) the activation parameters for the nonrotatory flapping process are identical to those for the nonflapping peptide rotation in the complexes anti-1 a,b,d-h, which indicates that the present multistep conformational transformation induced by the flapping motion is controlled by the rate-determining pyramidalization/depyramidalization (i.e., sp(2)/sp(3) interconversion) of the nitrogen atoms of the functionalities. The static and controllable molecular mobility of anti-1 bearing peptide linkers has been discussed by comparison with the dynamic behavior of its analogues anti-2-4 with flexible polymethylene linkers.