Role of chelate substituents and cis sigma-effect on the rate of ligand substitution at Pt(N-N-N) and Pt(N-N-C) centres.
Four complexes of the type [Pt(N-N-X)Cl](X = N or C) were tailor synthesized for mechanistic studies in methanol. The terdentate ligands included terpy, 4'-Ph-terpy, 4'-(2"-CF(3)-Ph)-terpy, and 4'-(2"'-CF(3)-Ph)-6-Ph-2,2'-bipy. The rate of substitution of the chloro ligand by thiourea, N,N'-dimethylthiourea, and N,N,N',N'-tetramethylthiourea was studied as a function of nucleophile concentration, temperature and pressure by using a stopped-flow technique. The observed pseudo-first-order rate constants for the substitution reactions obeyed the simple rate law k(obs) = k(2)[Nu]. Second-order kinetics and negative activation entropies and volumes support an associative substitution mechanism. At 298 K, the values of the second-order rate constant show a slight dependence on the nature of the moiety attached to the terpy ligand. Changing from a nitrogen sigma-donor to a carbon sigma-donor in the cis position, results in a deceleration of the substitution rate. The results suggest that the Pt-C bond in the cis position activates the metal centre in a different way than in the trans position.
Synthesis by ligand exchange, structural characterization, and aqueous chemistry of ortho-palladated oximes
Dimeric chloro-bridged ortho-palladated complexes of general formula [PdCl{C 6 H 4 (CR=NOH)-2}] 2 , where R=H, Me, Et, and Ph, were prepared via the ligand-exchange reaction starting from aryl oximes and cyclopalladated complexes of N,N-dimethylbenzylamine, ((dimethylamino)methyl)ferrocene, or benzophenone oxime. By reaction with various pyridine (Zpy), the dimers were converted into the corresponding monomers [PdCl{C 6 H 4 (CR=NOH)2}(Zpy)]
History of Amateurism in Men's Intercollegiate Athletics: The Continuance of a 19th-Century Anachronism in America
Claiming that American intercollegiate athletics are amateur at the end of the 20th century is an anachronism, for colleges in the 19th century took on professional characteristics. The upper-class British concept of amateurism did not work effectively in a more egalitarian and achievement-oriented American society. Hypocrisy resulted when colleges claimed amateurism while accepting such professional practices as hiring professional coaches, allowing athletes to play summer baseball for money, and paying athletes through grants-in-aid. Attempts to preserve amateurism, such as the Graham Plan in the 1930s and the Sanity Code in the 1940s and 1950s, yielded to the professional spirit. Thus, while Americans had generally rejected the upper-class British social hierarchy that fostered amateurism, they retained the name amateur, continuing the hypocrisy that had begun in the previous century.