40852-89-9Relevant academic research and scientific papers
Bimolecular chemistry of dimethylcarbene
Likhotvorik, Igor R.,Tippmann, Eric,Platz, Matthew S.
, p. 3049 - 3051 (2007/10/03)
A new non-nitrogenous precursor of dimethylcarbene has been synthesized. Photolysis of 10,10′-dimethyltricyclo[4.3.1.01,6]deca-2,4-diene in solution with 254 nm light produces dimethylcarbene. Previously unknown intermolecular reactions of dimethylcarbene have been observed.
Site specificity in molecular hydrogen elimination from photodissociation of propane at 157 nm
Wu,Lin,Lee,Yang
, p. 1793 - 1796 (2007/10/03)
Site effects on the molecular hydrogen elimination from propane at 157 nm excitation have been studied using the photofragment translational spectroscopic technique. Experimental results indicate that H2 elimination from the internal carbon of propane (2,2-elimination) is predominant while eliminations from the terminal carbon (1,1- and 1,3-elimination) and the vicinal carbons (1,2-elimination) are minor. The translational energy distributions obtained for these processes also show that the dynamics of H2 eliminations from different sites are significantly different. Relative branching ratios of the atomic hydrogen (H) and the molecular hydrogen (H2) elimination processes were also determined.
Hydrocarbon Activation by Gas-Phase Lanthanide Cations: Interaction of Pr+, Eu+, and Gd+ with Small Alkanes, Cycloalkanes, and Alkenes
Schilling, J. Bruce,Beauchamp, J. L.
, p. 15 - 24 (2007/10/02)
We describe ion beam studies of the interaction of gas-phase lanthanide ions, praseodymium (Pr+), europium (Eu+), and gadolinium (Gd+), with small alkanes, cycloalkanes, alkenes, and several oxygen-containing compounds.Only Gd+ is seen to activate C-H and C-C bonds of alkanes.The ground-state electronic configuration of Gd+ (4f75d16s1) is different from those of Pr+ (4f36s1) and Eu+ (4f76s1), leading to the conclusion that the f electrons play little part in the metal ion reactivity.Gd+ can be thought of as having two valence electrons, and indeed it reacts similarly to Sc+ and the other group 3 metal ions Y+ and La+, yielding products corresponding to elimination of hydrogen, alkanes, and alkenes.The elimination of neutral alkenes in the reaction of Gd+ with alkanes results in the formation of metal dialkyl or hydrido-alkyl complexes.This finding leads to estimates for the sum of two Gd+ ? bond dissociation energies of between 110 and 130 kcal/mol.Gd+ and Pr+ react readily with alkenes, yielding mostly dehydrogenation products along with smaller amounts of C-C bond cleavage products.Reactions of Gd+ and Pr+ with oxyen-containing species such as nitric oxide, formaldehyde, acetaldehyde, and acetone yield primarily the metal oxide ions and provide a lower limit for D(M+-O) of 179 kcal/mol, in good agreement with literature values of D(Pr+-O) = 188.4 +/- 5.2 kcal/mol and D(Gd+-O) = 181.0 +/- 4.4 kcal/mol.In keeping with the strong metal ? bonds, Gd+ is also seen to readily react with formaldehyde to eliminate CO and form GdH2+.
