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Direct Studies of 1,1-Diazenes. Syntheses, Infrared and Electronic Spectra, and Kinetics of the Thermal Decomposition of N-(2,2,6,6-Tetramethylpiperidyl)nitrene and N-(2,2,5,5-Tetramethylpyrrolidyl)nitrene
Hinsberg, William D.,Schultz, Peter G.,Dervan, Peter B.
, p. 766 - 773 (2007/10/02)
The syntheses, direct spectroscopic observation, and kinetics of thermal decomposition of the persistent 1,1-diazenes, N-(2,2,6,6-tetramethylpiperidyl)nitrene (4) and N-(2,2,5,5-tetramethylpyrrolidyl)nitrene (5) are reported.The electronic absorption spectrum of 4 at -78 deg C reveals a structured absorption for the n,?* transition: λmax = 543 nm, λ0,0 = 620 nm, and εmax = 18 +/- 3 in Et2O; λmax = 541 nm and λ0,0 = 610 in CH2Cl2; λmax = 526 nm and λ0,0 = 592 nm in i-PrOH.The electronic absorption spectrum of 1,1-diazene 5 at -78 deg C reveals a structured absorption band for the n,?* transition: λmax = 497 nm and λ0,0 = 572 nm and εmax = 20 +/- 3 in CH2Cl2; λmax = 487 nm and λ0,0 = 552 nm in i-PrOH.The infrared spectrum of 4 shows a strong absorption at 1595 cm-1 (R214N=14N stretch) and provides evidence that 1,1-diazene 4 has considerable N=N double-bond character in the ground state.The infrared spectrum of 5 shows a strong absorption at 1638 cm-1 (R214N=14N stretch).The unimolecular rate of thermal decomposition of 4 is sensitive to solvent, the rate increasing with decreasing solvent polarity (krel = 1.0, 1.7, 4.8 in THF, Et2O, and hexane, respectively).The activation parameters for the unimolecular fragmentation of 1,1-diazene 4 are as follows: log A = 11.6 +/- 0.5 and Ea = 16.9 +/- 0.7 kcal mol-1 in hexane; log A = 13.7 +/- 0.3 and Ea = 20.0 +/- 0.4 kcal mol-1 in Et2O; log A = 13.6 +/- 0.3 and Ea = 20.1 +/- 0.4 kcal mol-1 in THF.The activation parameters for the bimolecular dimerization of 4 are log A = 3.8 +/- 0.7 and Ea = 6.4 +/- 0.9 kcal mol-1 in CDCl3.The unimolecular rate of thermal decomposition of 5 is sensitive to solvent, the rate increasing with decreasing solvent polarity, krel = 1.0, 2.4, and 5.1 for THF, Et2O, and hexane, respectively.The activation parameters for the unimolecular fragmentation of 1,1-diazene 5 are as follows: log A = 10.9 +/- 0.3 and Ea = 16.8 +/- 0.5 kcal mol -1 in hexane; log A = 12.4 +/- 0.4 and Ea = 19.0 +/- 0.6 kcal mol-1 in Et2O; log A = 12.1 +/- 0.3 and Ea = 19.1 +/- 0.4 kcal mol-1 in THF.At -41.1 deg C the bimolecular rate constant for the dimerization of 5 is 8.5 * 10-5 L/(mol s), 90 times slower than that found for 4.The change from a six-membered to five-membered ring 1,1-diazene causes a shift to higher energy for the n,?* transition and a shift to increased wavenumber (cm-1) for the N=N stretching frequency, not unlike that of the isoelectronic ketones, tetramethylcyclohexanone and tetramethylcyclopentanone.Similar Ea values for the unimolecular thermal fragmentation of 4 and 5 may indicate the strain energy difference between 4 and 5 is also small.An approximate value of 30.5 kcal mol-1 for the heat of formation of the 1,1-diazene 5 is estimated, indicating the 1,1-diazene 5 has a higher heat of formation than...