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Metal-ligand bond enthalpy data can afford invaluable insights into important reaction patterns in organometallic chemistry and catalysis. In this paper, the Fe-O and Fe-S homolytic bond dissociation energies [ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s] of two series of para-substituted phenoxydicarbonyl(h 5 -cyclopentadienyl) iron [p-G-C 6 H 4 OFp (1)] and (para-substituted benzenethiolato)dicarbonyl(h 5 -cyclopentadienyl) iron [p-G-C 6 H 4 SFp (2)] were studied using Hartree-Fock and density functional theory (DFT) methods with large basis sets. In this study, Fp is (h 5 -C 5 H 5 )Fe(CO) 2 , and G are NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 . The results show that DFT methods can provide the best price/performance ratio and accurate predictions of ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s. The remote substituent effects on ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s [ΔΔH homo (Fe-O)'s and ΔΔH homo (Fe-S)'s] can also be satisfactorily predicted. The good correlations [r = 0.98 (g, 1), 0.98 (g, 2)] of ΔΔH homo (Fe-O)'s and ΔΔH homo (Fe-S)'s in series 1 and 2 with the substituent s p + constants imply that the para-substituent effects on ΔH homo (Fe-O)'s and ΔH homo (Fe-S)'s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔH homo (Fe-O)'s (1) and ΔΔH homo (Fe-S)'s (2) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes.

The purpose of this investigation was to examine comparable dimensions and linkages between child temperament and parenting styles with samples from Beijing, China and the western United States. Participants included 404 mothers and fathers from Beijing, China and 325 mothers and fathers from the western United States. Both mothers and fathers completed Buss and Plomin's (1984) EAS Temperament Scale as well as a spousal-report measure of parenting styles. Structural equation modelling was used to identify invariant (statistically comparable) factors for child temperament and parenting styles. Within-culture gender comparisons showed that Chinese fathers (relative to mothers) viewed their sons as being more active and sociable than daughters while US mothers (relative to fathers) rated their sons as being more active. Across-culture differences revealed that US parents (relative to Chinese parents) viewed children as more emotional while Chinese fathers (relative to US fathers) rated their children as more active. Similar and differential cultural patterns of linkages were also found between parenting styles and child temperament. Child emotionality was positively associated with authoritarian parenting in both cultures while child activity level was linked to more authoritative and less authoritarian parenting styles, but only in the Chinese sample. Finally, child sociability was found to be negatively linked to cross-gender patterns of authoritarian parenting in the US while mothers' and fathers' authoritarian parenting in China was linked to lower sociability in daughters only.