Asymmetric hydrogenation of alkenes with cationic iridium(I) complexes of 2-phosphino-1-aminoferrocene ligands

Iridium complexes with bidentate P,N ligands represent a class of catalysts that significantly expand the application range of asymmetric hydrogenation. New substrate classes, for which there have previously been no suitable catalysts, can now be efficiently hydrogenated in high conversion and enantioselectivity. These substrates are often of synthetic importance, thus iridium catalysis represents a significant advance in the field of asymmetric catalysis. Planar chiral ferrocenyl aminophosphine ligands in which both heteroatoms were directly bound to the cyclopentadienyl ring were prepared by BF3-activated lithiationsubstitution in the presence of a chiral diamine in 49-59% yield and 75-85% enantiomeric excess. Some of these ligands were recrystallized to enantiomeric purity via ammonium fluoroborate salt formation of the phosphine sulfide. A crystal structure of one of these compounds was obtained and features an intramolecular hydrogen bond between the nitrogen, hydrogen, and sulfur atoms. Neutralization, followed by desulfurization, provided the free ligands in enantiomeric purity. Iridium complexes with these ligands were formed via reaction with [Ir(COD)Clh followed by anion exchange with NaBArF. These complexes were successfully applied in homogeneous hydrogenation of several prochiral substrates, providing products in up to 92% enantiomeric excess. Variation of the dimethyl amino group to a pyrrolidine group had a negative effect on the selectivity of hydrogenation. Variation of the substituents on phosphorus to bulkier ortho-tolyl groups had a positive effect, while variation to the more electron rich dicyclohexyl phosphine had a negative effect on selectivity.

Nonsuicidal Self-Injury and Suicidal Behavior: A Latent Class Analysis among Young Adults

Although there is a general consensus among researchers that engagement in nonsuicidal self-injury (NSSI) is associated with increased risk for suicidal behavior, little attention has been given to whether suicidal risk varies among individuals engaging in NSSI. To identify individuals with a history of NSSI who are most at risk for suicidal behavior, we examined individual variability in both NSSI and suicidal behavior among a sample of young adults with a history of NSSI (N = 439, Mage = 19.1). Participants completed self-report measures assessing NSSI, suicidal behavior, and psychosocial adjustment (e.g., depressive symptoms, daily hassles). We conducted a latent class analysis using several characteristics of NSSI and suicidal behaviors as class indicators. Three subgroups of individuals were identified: 1) an infrequent NSSI/not high risk for suicidal behavior group, 2) a frequent NSSI/not high risk for suicidal behavior group, and 3) a frequent NSSI/high risk for suicidal behavior group. Follow-up analyses indicated that individuals in the ‘frequent NSSI/high risk for suicidal behavior’ group met the clinical-cut off score for high suicidal risk and reported significantly greater levels of suicidal ideation, attempts, and risk for future suicidal behavior as compared to the other two classes. Thus, this study is the first to identity variability in suicidal risk among individuals engaging in frequent and multiple methods of NSSI. Class 3 was also differentiated by higher levels of psychosocial impairment relative to the other two classes, as well as a comparison group of non-injuring young adults. Results underscore the importance of assessing individual differences in NSSI characteristics, as well as psychosocial impairment, when assessing risk for suicidal behavior.

Statement showing the totals of the quantity of each class of articles transported on the Welland Canal during the years ending on the 31st of December 1857-1861

Statement showing the totals of the quantity of each class of articles transported on the Welland Canal during the years ending on the 31st of December 1857-1861 and the amount of tolls collected thereon 2 ½ page, hand drawn chart), Dec. 31, 1861.