3506-84-1Relevant articles and documents
REACTIVITY OF LOW ENERGY EXCITED STATES. MECHANISTIC AND EXPLORATORY ORGANIC PHOTOCHEMISTRY
Zimmerman, Howard E.,Blinn, James R.
, p. 3237 - 3244 (1981)
The photochemistry of 3-methyl-3-(1'-naphthyl)-1-butene was investigated.Direct irradiation led to 1,1-dimethyl-2-(1'-naphthyl)cyclopropane as a primary photoproduct and 2-methyl-4-(1'-naphthyl)-1-butene as a secondary product.The quantum yield for the formation of the cyclopropane was 0.037.The corresponding triplet reaction was less efficient, with a quantum yield of 0.012, but still afforded the same product.The excited singlet rearrangement rate was determined by single photon counting; this proved to be 1kr = 5.9 x 105 sec-1.The total rate of S1 decay was determined as 1.59 x 107 sec-1 with a lifetime of 62.9 nsec.Thus, the lifetime of this rearranging system is quite similar to that of simple 1-alkylnaphthalenes (ca 65 nsec); and, the rate of di-?-methane rearrangement is the slowest known.Finally, the rate of radiationless decay of the singlet was found to be almost temperature independent between room temperature and 77 K.
Hydrogen-transfer reduction of α,β-unsaturated carbonyl compounds catalyzed by naphthyridine-functionalized N-heterocyclic carbene complexes
Huang, Hsiao-Ching,Ramanathan, Mani,Liu, Yi-Hong,Peng, Shie-Ming,Liu, Shiuh-Tzung
, (2017/07/25)
Substitution of silver complex of 2-chloro-7-(mesitylimidazolylidenylmethyl)naphthyridine (NpNHC) with palladium(II), rhodium(I) and iridium(I) metal precursors provided [Pd(C,N-NpNHC)(η3-allyl)](BF4) (5), RhCl(COD)(C-NpNHC) (6a) and IrCl(COD)(C-NpNHC) (6b), respectively. Abstraction of chloride from 6a and 6b with AgBF4 provided the chelation complexes [Rh(COD)(C,N-NpNHC)](BF4) (7a) and Ir(COD)(C,N-NpNHC)(BF4) (7b), respectively. All complexes were characterized using NMR and elemental analyses and the structural details of 5 and 6a were further confirmed using X-ray crystallography. In catalytic activity studies, complex 5 was found to be an effective catalyst in the hydrogen-transfer reduction of α,β-unsaturated carbonyl compounds into the corresponding saturated carbonyl compounds.
Preparation, hydrogen bonds, and catalytic activity in metal-promoted addition of arylboronic acids to enones of a rhodium complex containing an NHC ligand with an alcohol function
Penafiel, Itziar,Pastor, Isidro M.,Yus, Miguel,Esteruelas, Miguel A.,Olivan, Montserrat
, p. 6154 - 6161 (2012/10/29)
The complex RhCl(COD){3-benzyl-1-(2-hydroxy-2-phenylethyl)imidazol-2- ylidene} has been prepared by reaction of the dimer [Rh(μ-OMe)(COD)] 2 with 3-benzyl-1-(2-hydroxy-2-phenylethyl)imidazolium chloride and characterized by X-ray diffraction analysis. The structure reveals that 75% of the molecules are associated through intermolecular O-H...Cl hydrogen bonds between the OH group of the NHC substituent of one molecule and the chloride ligand of the adjacent molecule. This complex catalyzes the addition of arylboronic acids to cyclic and acyclic enones in anhydrous toluene. The alcohol function of the substituent of the NHC ligand plays the role assigned to water in previous cases.
