Assessing the performance of rotational spectroscopy in chiral analysis

The capabilities of rotational spectroscopy-based methods as tools to deliver accurate and precise chirality-sensitive information are still breaking ground, but their applicability in the challenging field of analytical chemistry is already clear. In this mini review, we explore the current abilities and challenges of two emergent techniques for chiral analysis based on rotational spectroscopy. For that, we will showcase the two methods (microwave 3-wave mixing and chiral tag rotational spectroscopy) while testing their performance to solve the absolute configuration and the enantiomeric excess of a blind sample containing a mixture of enantiomers of styrene oxide.

Two rotational spectroscopy methods are challenged to solve the absolute configuration and enantiomeric excess of a chiral mixture of unknown composition.     

Synthesis and activity of ruthenium alkylidene complexes coordinated with phosphine and N-heterocyclic carbene ligands

This paper reports the synthesis and characterization of a variety of ruthenium complexes coordinated with phosphine and N-heterocyclic carbene (NHC) ligands. These complexes include several alkylidene derivatives of the general formula (NHC)(PR(3))(Cl)(2)Ru=CHR', which are highly active olefin metathesis catalysts. Although these catalysts can be prepared adequately by the reaction of bis(phosphine) ruthenium alkylidene precursors with free NHCs, we have developed an alternative route that employs NHC-alcohol or -chloroform adducts as "protected" forms of the NHC ligands. This route is advantageous because NHC adducts are easier to handle than their free carbene counterparts. We also demonstrate that sterically bulky bis(NHC) complexes can be made by reaction of the pyridine-coordinated precursor (NHC)(py)(2)(Cl)(2)Ru=CHPh with free NHCs or NHC adducts. Two crystal structures are presented, one of the mixed bis(NHC) derivative (H(2)IMes)(IMes)(Cl)(2)Ru=CHPh, and the other of (PCy(3))(Cl)(CO)Ru[eta(2)-(CH(2)-C(6)H(2)Me(2))(N(2)C(3)H(4))(C(6)H(2)Me(3))], the product of ortho methyl C-H bond activation. Other side reactions encountered during the synthesis of new ruthenium alkylidene complexes include the formation of hydrido-carbonyl-chloride derivatives in the presence of primary alcohols and the deprotonation of ruthenium vinylcarbene ligands by KOBu(t). We also evaluate the olefin metathesis activity of NHC-coordinated complexes in representative RCM and ROMP reactions.     

The Effects of Self-Regulation,Motivation, Anxiety,and Attributions on Mathematics Achievement for Fifth and Sixth Grade Students

For this quantitative study, a total of n = 761 students (58.1% female) from selected fifth- and sixth-grade mathematics classrooms in Alabama were surveyed in order to investigate the relationships between self-regulated learning, motivation, anxiety, attributions and achievement in mathematics. Data analyses revealed that significant contributions are made by motivation and anxiety on both test score and mathematics grade for fifth grade students. Specific factors (e.g., self-efficacy, worry, other, and failure) were related to academic performance while failure attribution was significantly related to mathematics grade. As for sixth grade students, data analyses showed relationships exist between motivation, anxiety and academic performance with specific factors (i.e., self-efficacy, intrinsic value, and worry) significantly predicting both test score and mathematics grade for sixth graders. The findings underlie the importance of motivation and anxiety for students and how these constructs interact to facilitate self-regulation over the course of developing expertise in a domain, such as mathematics.