Probing the mechanistic and energetic basis for the Weak-Link approach to supramolecular coordination complexes

Through the Weak-Link Synthetic Approach, the unsymmetric hemilabile ligand, 1,4-bis-(2-diphenylphosphinoethoxy)naphthalene (7), has been used to prepare binuclear Rh(I) macrocycles in a two-step fashion. The intermediate structure, [(μ²,η¹:η⁴:η¹-(1,4-bi s(2-(diphenylphosphino)ethoxy)naphthalene))₂Rh₂] [BF₄]₂ (8), and several macrocyclic complexes, [(μ²-1,4-bis(2-(diphenylphosphino)ethoxy)naphthalene)₂R h₂(CH₃CN)₄] [BF₄]₂ (9), [(μ²-1,4-bis-(2-(diphenylphosphino)ethoxy)naphthalene)₂ Rh₂(CO)₆][BF₄]₂ (10), and [(μ²-1,4-bis(2-(diphenylphosphino)ethoxy)naphthalene)₂( CO)₂Rh₂(CH₃CN)₂][BF₄] ₂ (11), are reported herein. Additionally, the mononuclear Rh(I) complexes, [(η¹:η⁴:?η¹-1,4-bis(2-(diphenylphos phino)ethoxy)-naphthalene)Rh] [BF₄] (12) and [(η¹:η¹-1,4-bis(2-(diphenylphosphino)ethoxy)naphth alene)-(CO)Rh(CH₃CN)] [BF₄] (13), were isolated and fully characterized. Single-crystal X-ray diffraction structures of 8, 9 (cis-, anti-), 11, and 12 were determined. 2-D solution NMR studies and the solid-state crystal structures of 8 and 12 suggest that the arenes bind to Rh(I) in predominantly an η⁴-fashion. The conversion of dimer 8 into monomer 12 was monitored under a variety of conditions. The kinetic investigation of this process as a function of temperature with a series of phosphine-based ligands present has afforded the thermo-chemical parameters of this conversion, which are consistent with an associative mechanism. Significantly, this work represents the first study aimed at gaining mechanistic insight into the conversion of the binuclear intermediates into the mononuclear products formed in the Weak-Link Approach. The high activation barrier and associative nature of this step is what allows one to efficiently synthesize targeted macrocyclic and higher-ordered structures via the approach.