Reaction of the new highly electron-donating PNP ligand [2,6-bis-(di-tert-butylphosphinomethyl)pyridine] (1) with [Rh(COE) 2 Cl] 2 (COE ) cyclooctene) at room temperature resulted in formation of the neutral Rh(I) complex [Rh(PNP)Cl] (2). Unsaturated cationic complexes [Rh(PNP)(CH 3 CN)]BF 4 (3) and [Rh(PNP)(C 2 H 4 )]SO 3 CF 3 (4) were obtained in reaction of 1 with [(COE) 2 Rh(CH 3 CN) 2 ]BF 4 and [(C 2 H 4 ) 2 Rh(THF) 2 ]SO 3 CF 3 , respectively. Upon reaction of the PNP ligand 1 with [Ir(COE) 2 Cl] 2 , facile vinylic C-H activation takes place, yielding the hydrido-vinyl complex [ClIr(PNP)(H)(C 8 H 13 )] ( 5). Also, coordination of ligand 1 to the cationic iridium complex [Ir(COD) 2 ]BF 4 (COD ) cyclooctadiene) in RCN (R ) CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 ) led to iridium insertion into a vinylic C-H bond, resulting in complexes [(RCN)-Ir(PNP)(H)(C 8 H 11 )]BF 4 (6a-c). The hydrido-vinyl complexes 6a,c readily react with H 2 (2 atm) at room temperature, affording the iridium dihydride complexes [(RCN)Ir(PNP)-(H) 2 ]BF 4 (R ) CH 3 , C(CH 3 ) 3 ) (7a,b).
The article contains sections titled: 1. Introduction 2. Organic Hydroperoxides 2.1. Definition 2.2. Physical and Chemical Properties 2.3. Production and Commercial Products 3. Dialkyl Peroxides 3.1. Definition 3.2. Physical and Chemical Properties 3.3. Production and Commercial Products 4. Diacyl Peroxides 4.1. Definition 4.2. Physical and Chemical Properties 4.3. Production and Commercial Products 5. Peroxycarboxylic Acids 5.1. Definition 5.2. Physical and Chemical Properties 5.3. Production and Commercial Products 6. Peroxycarboxylic Acid Esters 6.1. Definition 6.2. Physical and Chemical Properties 6.3. Production and Commercial Products 7. Peroxycarbonates 7.1. Definition 7.2. Physical and Chemical Properties 7.3. Production and Commercial Products 8. Peroxyketals 8.1. Definition 8.2. Physical and Chemical Properties 8.3. Production and Commercial Products 9. Ketone Peroxides 9.1. Definition 9.2. Physical and Chemical Properties 9.3. Production and Commercial Products 10. Analytical Determination 11. Uses 11.1. Polymer Manufacture 11.1.1. PVC 11.1.2. LDPE (Low‐Density Polyethylene) 11.1.3. cr‐PP (cr‐Polypropylene) 11.1.4. PS (Polystyrene) 11.1.5. Poly(meth)acrylates (PMMA) 11.1.6. Others 11.2. Polymer Processing 11.2.1. UP Curing 11.2.2. Cross‐Linking of Polymers (XL) 11.3. Nonpolymer Applications 12. Safety Hazards and Legal Aspects 13. Transportation and Storage 14. Toxicology and Occupational Health
A new synthetic methodology for the preparation of donor ± bridge ± acceptor compounds incorporating a porphyrin donor and an allaromatic oligo(diazaphenylene) bridge is introduced. This approach allows the controlled preparation of photosynthetic model compounds with well-defined spacer structure and properties. The synthesis of the porphyrin ± flavin dyads 1 a ± c is described to exemplify the strategy. This type of structure has a number of interesting spectroscopic and photophysical properties. The aromatic bridge results in a well-defined donor ± acceptor distance; it can favor conjugation and at the same time be nonabsorbing in the visible and near-UV range. The choice of a flavin as the acceptor unit opens the way to a spectroscopic study by excitation of the acceptor in addition to the usual porphyrin donor excitation. Based on these premises, a spectroscopic, photophysical and semiempirical study of the dyad 1 a has been performed in three solvents of varying polarity. The results demonstrate energy transfer from flavin to porphyrin with unit efficiency at high solvent polarity. In solvents of medium polarity an additional internal conversion pathway is opened following excitation of the flavin moiety. Spectroscopic, cyclovoltammetric, and semiempirical results all suggest that this pathway involves the intermediate population of a short-lived charge-separated state.
Tetra-p-tolyl and tetrathienyl substitution of manganese(III) porphyrins in charge-transfer compounds with organic acceptors like tetracyanoethylene is used to modify molecular packing of ferrimagnetically correlated chains in the solid. Ferri-and antiferromagnetically ordered compounds and also borderline situations are realized. The strong in¯uence of the solvent used for crystal growth is exempli® ed.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.