The crystal and molecular structure of 18-Crown-6 HgC12 and 18-Crown-6 Cdc12

Hg(18-Crown-6)C12 and Cd(18-Crown-6)C12 are isostructura1, space group Cl~ Z = 2. For the mercury compound, a = 10.444(2) A° , b = 11. 468(1) A° , c = 7.754(1) A° , a = 90.06(1)°, B = 82.20(1)°, Y = 90.07(1)°, Dobs = 1.87, Dca1c = 1.93, V = 920.05 13, R = 4.66%. For the cadmium compound, 000 a = 10.374(1) A, b = 11.419(2) A, c = 7.729(1) A, a = 89.95(1)°, B = 81.86(2)°, Y = 89.99(1)°, Dobs = 1.61, Dcalc = 1.64, V = 906.4613, R = 3.95%. The mercury and cadmium ions exhibit hexagonal bipyramidal coordination, with the metal ion located on a centre of symmetry in the plane of the oxygen atoms. The main differences between the two structures are an increase in the metal-oxygen distance and a reduction in the metalchloride distance when the central ion changes from Cd2+ to Hg2+. These differences may be explained in terms of the differences in hardness or softness of the metal ions and the donor atoms.

Synthesis, Catalysis and Stoichiometric Reactivity of Mo Imido Complexes

The syntheses, catalytic reactivity and mechanistic investigations of novel Mo(IV) and Mo(VI) imido systems is presented. Attempts at preparing mixed bis(imido) Mo(IV) complexes of the type (RN)(R′N)Mo(PMe3)n (n = 2 or 3) derived from the mono(imido) complexes (RN)Mo(PMe3)3(X)2 (R = tBu (1) or Ar (2); X = Cl2 or HCl, Ar=2,6-iPr2C6H3) are also described. The addition of lithiated silylamides to 1 or 2 results in the unexpected formation of the C-H activated cyclometallated complexes (RN)Mo(PMe3)2(η2-CH2PMe2)(X) (R = Ar, X = H (3); R = tBu, X = Cl (4)). Complexes 3 and 4 were used in the activation of R′E-H bonds (E = Si, B, C, O, P; R′ = alkyl or aryl), which typically give products of addition across the M-C bond of the type (RN)Mo(PMe3)3(ER′)(X) (4). In the case of 2,6-dimethylphenol, subsequent heating of 4 (R = Ar, R′ = 2,6-Me2C6H3, E = O) to 50 °C results in C-H activation to give the cyclometallated complex (ArN)Mo(PMe3)3(κ2-O,C-OPh(Me)CH2) (5). An alternative approach was developed in synthesizing the mixed imido complex (ArN)(tBuN)Mo(PMe3)(η2-C2H4) (6) through EtMgBr reduction of (ArN)(tBuN)MoCl2(DME) in the presence of PMe3. Complex 6 reacts with various hydro- and chlorosilanes to give β-agostic silylamido complexes and in one case, when Me2SiHCl is the silane, leads to the silanimine complex (tBuN)Mo(η2-SiMe2-NAr)(Et)(η2-C2H4) (7). Mechanistic studies on the formation of the Mo(VI) tris(silyl) complex (tBuN)Mo(SiHPh)(H){(μ-NtBu)(SiHPh)}(PMe3)2 (8) were done from the addition of three equivalents of PhSiH3 to (tBuN)Mo(PMe3)(η2-C2H4), resulting in identification of β- and γ-agostic SiH…Mo intermediates. The reactivity of complex 8 towards ethylene and nitriles was studied. In both cases coupling of unsaturated substrates with the Mo-Si bond of the metalacycle was observed. In the case of nitriles, insertion into the 4-membered disilaazamolybdacycle results in complexes of the type (tBuN)Mo{(κ2-Si,C-SiHPh-NtBu-SiHPh-N=C(R)}(PMe3)2. Catalytic hydrosilylation of carbonyls mediated by the β-agostic silylamido complex (ArN)2Mo(η3-NtBu-SiMe2-H)(H) (9) was investigated. Stoichiometric reactions with organic substrates showed that catalysis with 9 does not proceed via the conventional insertion of substrate into the Mo-H bond.

VOCATIONAL INTERESTS: CONSTRUCT VALIDITY AND MEASUREMENT

This dissertation addressed several questions relevant to vocational interests and personality characteristics, examining (a) the roles of personality, vocational interests, and sexual fantasies in defining a general factor of Masculinity/Femininity (M/F) (Study 1), (b) the validity of a new measure of vocational interests (Study 2), and (c) the individual difference characteristics that discriminate between students in various academic majors, and that predict academic outcomes (Study 3). In Study 1, vocational interests, personality, and sexual fantasies were examined to find whether these variables would yield a general Masculinity/Femininity (M/F) factor, and whether that factor would still emerge when controlling for participant sex. The results of Study 1 revealed that a general factor of M/F did emerge. When sex was removed, the loadings of vocational interests decreased from high to very low, suggesting that the link of vocational interests with other indicators of M/F is mainly due to sex differences in these variables. The purpose of Study 2 was to validate the Oregon Vocational Interest Scales (ORVIS), a new public domain vocational interests questionnaire designed to measure eight vocational interest scales. ORVIS scores obtained in a college and community sample were compared with those of two personality measures and two cognitive ability tests. Results from this study showed that the ORVIS scales were reliable and showed good construct validity. The purpose of Study 3, using the ORVIS along with the HEXACO-PI and tests of cognitive ability, was to examine the individual difference characteristics of students in different academic majors, and to use the congruence between a student's academic major and vocational interests as a predictor of academic outcomes, such as GPA, academic major change, and satisfaction with major. The results of Study 3 revealed that students in different academic majors show theoretically meaningful differences in personality, abilities, and interests. Conscientiousness and math ability were found to be the best predictors of academic outcomes. However, congruence between major and interests did not add significant predictive validity to any of these outcomes beyond personality and ability. Together, these three studies show the role of vocational interests in defming MlF and in predicting various academic outcomes.

Examining the Nature of Published Research About Mentoring in Higher Education

The various forms of mentoring relationships in higher education have all proven to be valuable, offering numerous benefits to mentors and protégés. Research into mentoring provides critical insight into aspects of these relationships, which can be used to advance theoretical and practical understandings of the topic. However, little is known about the methodological characteristics of the mentoring research itself. Using descriptive quantitative content analysis, I examined five years of articles published in five scholarly journals to determine the prevalence of research about mentoring in higher education. Not surprisingly, the prevalence of these articles differed significantly among journals in higher education (1.07% to 3.13%) compared to the considerably higher prevalence rate of 53.15% for the mentoring journal, Mentoring & Tutoring [χ2 (4, N = 82) = 143.98, p < .01]. I also report findings related to the prevalence of different empirical research traditions, research designs, and data sources, as well as various populations, such as faculty members or graduate students who serve as mentors or protégés. Given the limited number of mentoring articles published in higher education journals, I was unable to compare methodological characteristics across journals. Implications for theory, research, and practice in the area of mentoring in higher education are also suggested. Understanding the methodological characteristics of the current literature allows researchers to tailor their current studies by either continuing with existing trends in methodological approaches or seeking opportunities to incorporate under-utilized research traditions, designs, or data sources, with the aim of continuing to improve mentoring knowledge and outcomes.