Cationic zirconium hydrides supported by an NNNN-type macrocyclic ligand: synthesis, structure, and reactivity.

An air- and light-sensitive, but thermally stable tris[(trimethylsilyl)methyl]zirconium complex containing an NNNN-type macrocyclic ligand [Zr(Me3TACD)(CH2SiMe3)3] (1; Me3TACD = Me3[12]aneN4: 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane) was prepared by reacting [Zr(CH2SiMe3)4] with (Me3TACD)H. Reaction of the zirconium tris(alkyl) 1 with a Lewis or Brønsted acid gave a dialkyl cation with a weakly coordinating anion [Zr(Me3TACD)(CH2SiMe3)2][A] [A = Al{OC(CF3)3}4 (2a), B{3,5-C6H3(CF3)2}4 (2b), B(3,5-C6H3Cl2)4 (2c), and BPh4) (2d)]. Hydrogenolysis of 2a-2c resulted in the formation of the dinuclear tetrahydride dication [{Zr(Me3TACD)(μ-H)2}2][A]2 (3a-3c).

Rare-earth metal allyl and hydrido complexes supported by an (NNNN)-type macrocyclic ligand: synthesis, structure, and reactivity toward biomass-derived furanics.

The preparation and characterization of a series of neutral rare-earth metal complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(2)] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane anion (Me(3)TACD(-)) are reported. Upon treatment of the neutral allyl complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(2)] with Brønsted acids, monocationic allyl complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(thf)(2)][B(C(6)X(5))(4)] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me(3)TACD)H(2)](n) (Ln=Y, n=3; La, n=4; Sm).

[Prolactin producing hypophyseal carcinoma. Case report of an extremely rare metastatic tumor].

A 59-year-old male patient was transnasally operated on because of a pituitary adenoma with hypopituitarism. A second operation and X-ray therapy followed a half year later due to recurrent tumor. Both neoplasmas were classified as sparsely granulated prolactin cell adenomas.