Oxidative Addition of a Mechanically Entrapped C(sp)–C(sp) Bond to a Rhodium(I) Pincer Complex

Abstract

By use of a macrocyclic phosphinite pincer ligand and bulky substrate substituents, we demonstrate how the mechanical bond can be leveraged to promote the oxidative addition of an interlocked 1,3‐diyne to a rhodium(I) center. The resulting rhodium(III) bis(alkynyl) product can be trapped out by reaction with carbon monoxide or intercepted through irreversible reaction with dihydrogen, resulting in selective hydrogenolysis of the C−C σ‐bond.

Syntheses, Structures, Reactivities, and Dynamic Properties of Gyroscope-like Complexes Consisting of Rh(CO)(X) or Rh(CO)2(I) Rotators and Cage-likeTransAliphatic Dibridgehead Diphosphine Stators

“…Finally, there is notable recent work involving other sterically constrained rhodium­(I) environments. − The most relevant features a series of complexes with phosphine pincer ligands that are connected by an additional (CH 2 ) 14 bridge, as reported by Chaplin and exemplified by 16 in Scheme . Ligands that occupy the cavity can show unique reactivity compared to unbridged analogues, providing further motivation for the continued development of the complexes in Schemes –.…”

Observation of the Low‐Frequency Spectrum of the Water Trimer as a Sensitive Test of the Water‐Trimer Potential and the Dipole‐Moment Surface

“…While the water dimer is the ideal candidate to test the accuracy of the water potential for an accurate description of two‐body interaction, the water trimer is the obvious candidate to test the three‐body interactions, which are essential to accurately describe bulk water and ice. Initial studies focused on the accurate determination of an accurate water‐dimer PES . The cyclic equilibrium structure of the water trimer is significantly stabilized by three‐body interactions, which will aid in incorporating cooperativity into the description of water models.…”