TY - JOUR
T1 - Tuning the Latency by Anionic Ligand Exchange in Ruthenium Benzylidene Phosphite Complexes
AU - Alassad, Nebal
AU - Phatake, Ravindra S.
AU - Baranov, Mark
AU - Reany, Ofer
AU - Lemcoff, N. Gabriel
N1 - Publisher Copyright:
© 2023 by the authors.
PY - 2023/11
Y1 - 2023/11
N2 - Recently discovered cis-dichloro benzylidene phosphite complexes are latent catalysts at room temperature and exhibit exceptional thermal and photochemical activation behavior in olefin metathesis reactions. Most importantly, the study of these catalysts has allowed their introduction in efficient 3-D printing applications of ring-opening metathesis derived polymers and the control of chromatically orthogonal chemical processes. Moreover, their combination with plasmonic Au-nanoparticles has given rise to novel smart materials that are responsive to light. Given the importance of the ligand shell in the initiation and reactivity behavior of this family of complexes, we set out to investigate the effect of anionic ligand exchange. Thus, we report herein two new ruthenium benzylidene benzylphosphite complexes where the chloride anionic ligands have been replaced by bromide and iodide anions (cis-Ru-Phos-Br2 & cis-Ru-Phos-I2). The thermal and photochemical activations of these dormant catalysts in a variety of ring-closing and ring-opening metathesis polymerization (RCM and ROMP) reactions were thoroughly studied and compared with the previously known chloride precatalyst. Photochemical RCM studies provided similar results, especially in non-hindered reactions, with the UV-A wavelength being the best in all cases. On the other hand, the thermal activation profile exposed that the anionic ligand significantly affects reactivity. Notably, cis-Ru-Phos-I2 disclosed particularly impressive initiation efficiency compared to the other members of the family.
AB - Recently discovered cis-dichloro benzylidene phosphite complexes are latent catalysts at room temperature and exhibit exceptional thermal and photochemical activation behavior in olefin metathesis reactions. Most importantly, the study of these catalysts has allowed their introduction in efficient 3-D printing applications of ring-opening metathesis derived polymers and the control of chromatically orthogonal chemical processes. Moreover, their combination with plasmonic Au-nanoparticles has given rise to novel smart materials that are responsive to light. Given the importance of the ligand shell in the initiation and reactivity behavior of this family of complexes, we set out to investigate the effect of anionic ligand exchange. Thus, we report herein two new ruthenium benzylidene benzylphosphite complexes where the chloride anionic ligands have been replaced by bromide and iodide anions (cis-Ru-Phos-Br2 & cis-Ru-Phos-I2). The thermal and photochemical activations of these dormant catalysts in a variety of ring-closing and ring-opening metathesis polymerization (RCM and ROMP) reactions were thoroughly studied and compared with the previously known chloride precatalyst. Photochemical RCM studies provided similar results, especially in non-hindered reactions, with the UV-A wavelength being the best in all cases. On the other hand, the thermal activation profile exposed that the anionic ligand significantly affects reactivity. Notably, cis-Ru-Phos-I2 disclosed particularly impressive initiation efficiency compared to the other members of the family.
KW - Ru-phosphite complexes
KW - anionic ligands
KW - olefin metathesis
KW - reaction kinetics
UR - http://www.scopus.com/inward/record.url?scp=85178300868&partnerID=8YFLogxK
U2 - 10.3390/catal13111411
DO - 10.3390/catal13111411
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AN - SCOPUS:85178300868
SN - 2073-4344
VL - 13
JO - Catalysts
JF - Catalysts
IS - 11
M1 - 1411
ER -