ABSTRACT
The rational development of homogeneous catalytic systems for selective aerobic oxidations of organics has been hampered by the limited available knowledge of how oxygen reacts with important organometallic intermediates. Recently, several mechanisms for oxygen insertion into late transition metal-hydride bonds have been described. Contributing to this nascent understanding of how oxygen reacts with metal-hydrides, a detailed mechanistic study of the reaction of oxygen with the IrIII hydride complex (dmPhebox)Ir(OAc)(H) (1) in the presence of acetic acid, which proceeds to form the IrIII complex (dmPhebox)Ir(OAc)2(OH2) (2), is described. The evidence supports a multifaceted mechanism wherein a small amount of an initially formed metal hydroperoxide proceeds to generate a metal-oxyl species that then initiates a radical chain reaction to rapidly convert the remaining IrIII-H. Insight into the initiation step was gained through kinetic and mechanistic studies of the radical chain inhibition by BHT (butylated hydroxytoluene). Computational studies were employed to contribute to a further understanding of initiation and propagation in this system.
ABSTRACT
BACKGROUND: A body of epidemiological studies has examined football injuries and associated risk factors among collegiate athletes. However, few existing studies specifically analyzed injury risk in terms of initial or subsequent injuries. PURPOSE: To determine athlete-exposures (AEs) and rates of initial and subsequent injury among collegiate football athletes. STUDY DESIGN: Descriptive epidemiological study. METHODS: Injury and exposure data collected from collegiate football players from two Division I universities (2007-2011) were analyzed. Rate of initial injury was calculated as the number of initial injuries divided by the total number of AEs for initial injuries, while the rate for subsequent injury was calculated as the number of subsequent injuries divided by the total number of AEs for subsequent injury. Poisson regression was used to determine injury rate ratio (subsequent vs initial injury), with adjustment for other covariates. RESULTS: The total AEs during the study period were 67,564, resulting in an overall injury rate of 35.2 per 10,000 AEs. Rates for initial and subsequent injuries were 31.7 and 45.3 per 10,000 AEs, respectively, with a rate ratio (RR) of 1.4 for rate of subsequent injury vs rate of initial injury (95% CI, 1.1-1.9). Rate of injury appeared to increase with each successive injury. RR during games was 1.8 (95% CI, 1.1-3.0). The rate of subsequent injuries to the head, neck, and face was 10.9 per 10,000 AEs, nearly double the rate of initial injuries to the same sites (RR = 2.0; 95% CI, 1.1-3.5). For wide receivers, the rate of subsequent injuries was 2.2 times the rate of initial injuries (95% CI, 1.3-3.8), and for defensive linemen, the rate of subsequent injuries was 2.1 times the rate of initial injuries (95% CI, 1.1-3.9). CONCLUSION: The method used in this study allows for a more accurate determination of injury risk among football players who have already been injured at least once. Further research is warranted to better identify which specific factors contribute to this increased risk for subsequent injury.
