Neutral and Cationic Rare Earth Metal Alkyl and Benzyl Compounds with the 1,4,6-Trimethyl-6-pyrrolidin-1-yl-1,4-diazepane Ligand and Their Performance in the Catalytic Hydroamination/Cyclization of Aminoalkenes

A new neutral tridentate 1,4,6-trimethyl-6-pyrrolidin-1-yl-1,4-diazepane (L) was prepared. Reacting L with trialkyls M(CH2SiMe3)3(THF)2 (M = Sc, Y) and tribenzyls M(CH2Ph)3(THF)3 (M = Sc, La) yielded trialkyl complexes (L)M(CH2SiMe3)3 (M = Sc, 1; M = Y, 2) and tribenzyl complexes (L)M(CH2Ph)3 (M = Sc, 3; M = La, 4). Complexes 1 and 2 can be converted to their corresponding ionic compounds [(L)M(CH2SiMe3)2(THF)][B(C6H5)4] (M = Sc, Y) by reaction with [PhNMe2H][B(C6H5)4] in THF. Complexes 3 and 4 can be converted to cationic species [(L)M(CH2Ph)2]+ by reaction with [PhNMe2H][B(C6F5)4] in C6D5Br in the absence of THF. The neutral complexes 1-4 and their cationic derivatives were studied as catalysts for the hydroamination/cyclization of 2,2-diphenylpent-4-en-1-amine and N-methylpent-4-en-1-amine reference substrates and compared with ligand-free Sc, Y, and La neutral and cationic catalysts. The most effective catalysts in the series were the cationic L-yttrium catalyst (for 2,2-diphenylpent-4-en-1-amine) and the cationic lanthanum systems (for N-methylpent-4-en-1-amine). For the La catalysts, evidence was obtained for release of L from the metal during catalysis.

Yttrium alkyl complex with a linked bis(amidinate) ancillary ligand

The dilithium salt of a linked bis(amidinate) dianionic ligand, Li2[Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3] (1), was prepared by reaction of dilithiated N,N'-bis(trimethylsilyl)-1,3-diaminopropane with benzonitrile. Reaction of 1 with YCl3(THF)3.5 gave [Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3]YCl(THF)2 (2), which, by reaction with Li[CH(SiMe3)2], was converted to the alkyl complex [Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3]Y[CH(SiMe3)2](THF) (3). A structure determination of 3 showed that linking together the amidinate functionalities opens up the coordination sphere to allow the bonding of an additional molecule of THF not present in the unbridged bis(amidinate) analogue [PhC(NSiMe3)2]2Y[CH(SiMe3)2].

Theotonio dos Santos (1936-2018), the revolutionary intellectual who pioneered dependency theory

This article analyzes the origins and development of the dependency theory through the life and work of Theotonio Dos Santos. His formative years at the academy and his early political activism in Brazil are examined, particularly, his time at the University of Brasilia with Vania Bambirra, Ruy Mauro Marini and André Gunder Frank ("the quartet"). This is followed by a discussion about their years of exile in Chile where the quartet regrouped at the Center for Socio-Economic Studies (ceso) of the University of Chile, and where they wrote their founding texts on dependency theory. Chile provided fertile ground for the development of this theory due to its intellectual climate, institutionality, and the country's political transformations in the late 1960s and early 1970s. The military overthrow of the Allende government on that fateful September 11th, 1973 forced the quartet once again into exile. The article continues with an analysis of Dos Santos' writings during his exile in Mexico and then back in Brazil. During this period he became involved with world system theory which culminated in the publication of his extensive trilogy on the contemporary crisis of capitalism and social theory

Pseudoneoplastic lesions of the testis and paratesticular structures

Pseudotumors or tumor-like proliferations (non-neoplastic masses) and benign mimickers (non-neoplastic cellular proliferations) are rare in the testis and paratesticular structures. Clinically, these lesions (cysts, ectopic tissues, and vascular, inflammatory, or hyperplastic lesions) are of great interest for the reason that, because of the topography, they may be relevant as differential diagnoses. The purpose of this paper is to present an overview of the pseudoneoplasic entities arising in the testis and paratesticular structures; emphasis is placed on how the practicing pathologist may distinguish benign mimickers and pseudotumors from true neoplasia. These lesions can be classified as macroscopic or microscopic mimickers of neoplasia