K-Ar and 40Ar/39Ar ages of dikes emplaced in the onshore basement of the Santos Basin, Resende area, SE Brazil: implications for the South Atlantic opening and tertiary reactivation

New K-Ar and Ar-40/Ar-39 data of tholeiitic and alkaline dike swarms from the onshore basement of the Santos Basin (SE Brazil) reveal Mesozoic and Tertiary magmatic pulses. The tholeiitic rocks (basalt, dolerite, and microgabbro) display high TiO2 contents (average 3.65 wt%) and comprise two magmatic groups. The NW-oriented samples of Group A have (La/Yb)N ratios between 15 and 32.3 and range in age from 192.9 +/- 2.2 to 160.9 +/- 1.9 Ma. The NNW-NNE Group B samples, with (La/Yb)(N) ratios between 7 and 16, range from 148.3 +/- 3 to 133.9 +/- 0.5 Ma. The alkaline rocks (syenite, trachyte, phonolite, alkaline basalts, and lamprophyre) display intermediate-K contents and comprise dikes, plugs, and stocks. Ages of approximately 82 Ma were obtained for the lamprophyre dikes, 70 Ma for the syenite plutons, and 64-59 Ma for felsic dikes. Because Jurassic-Early Cretaceous basic dikes have not been reported in SE Brazil, we might speculate that, during the emplacement of Group A dikes, extensional stresses were active in the region before the opening of the south Atlantic Ocean and coeval with the Karoo magmatism described in South Africa. Group B dikes yield ages compatible with those obtained for Serra Geral and Ponta Grossa magmatism in the Parana Basin and are directly related to the breakup of western Gondwana. Alkaline magmatism is associated with several tectonic episodes that postdate the opening of the Atlantic Ocean and related to the upwelling of the Trindade plume and the generation of Tertiary basins southeast of Brazil. In the studied region, alkaline magmatism can be subdivided in two episodes: the first one represented by lamprophyre dykes of approximately 82 Ma and the second comprised of felsic alkaline stocks of approximately 70 Ma and associated dikes ranging from 64 to 59 Ma. (c) 2005 Elsevier Ltd. All rights reserved.

Nitrenes, diradicals, and ylides. Ring expansion and ring opening in 2-quinazolylnitrenes

Tetrazolo[1,5-a] quinazoline (9) is converted to 2-azidoquinazoline (10) on sublimation at 200 degrees C and above, and the azide-tetrazole equilibrium is governed by entropy. 2-Quinazolylnitrenes 11 and 27 and/ or their ring expansion products 14 and 29 can undergo type I (ylidic) and type II (diradicaloid) ring opening. Argon matrix photolysis of 9/10 affords 2-quinazolylnitrene (11), which has been characterized by ESR, UV, and IR spectroscopy. A minor amount of a second nitrene, formed by rearrangement or ring opening, is also observed. A diradical (19) is formed rapidly by type II ring opening and characterized by ESR spectroscopy; it decays thermally at 15 K with a half-life of ca. 47 min, in agreement with its calculated facile intersystem crossing (19T -> 19OSS) followed by facile cyclization/rearrangement to 1-cyanoindazole (21) (calculated activation barrier 1- 2 kcal/mol) and N-cyanoanthranilonitrile (22). 21 and 22 are the isolated end products of photolysis. 21 is also the end product of flash vacuum thermolysis. An excellent linear correlation between the zero-field splitting parameter D (cm(-1)) and the spin density F on the nitrene N calculated at the B3LYP/EPRIII level is reported (R-2 = 0.993 for over 100 nitrenes). Matrix photolysis of 3-phenyltetrazolo[1,5-a] quinazoline (25) affords the benzotriazacycloheptatetraene 29, which can be photochemically interconverted with the type I ring opening product 2-isocyano-alpha-diazo-alpha- phenyltoluene (33) as determined by IR and UV spectroscopy. The corresponding carbene 37, obtained by photolysis of 33, was detected by matrix ESR spectroscopy.