The Pb isotope composition of polyformational Mesozoic igneous rocks of the Ketkap–Yuna igneous province (KYIP) and lower crustal metamorphic rocks of the Batomga granite–greenstone area (the complex of the KYIP basement) of the Aldan Shield was studied for the first time. Based on the data obtained, several types of material sources participating in petrogenetic processes were distinguished. The mantle source identified as PREMA is registered in most of the igneous formations and predominates in mafic alkaline rocks. According to the isotope characteristics, the upper crustal source corresponds to a source of the “Orogen” type by the model of “plumbotectonics” or to the average composition of the continental crust by the Stacey–Kramers model. The lower crust is the third material source; however, the type of lower crustal protolith involved in the igneous process is still not defined, which makes difficult to estimate its role in the petrogenetic processes.

The paper presents new data on age, geochemistry, and Sr and Nd isotope composition of rocks from the Akatui massif and comagmatic rocks from the lower unit of the Kailas Formation (Akatui volcano-plutonic association), localized within the Aleksandrovskii Zavod depression. The amphibole Ar-40/Ar-39 age date the monzogabbro of the early phase of the Akatui massif at 154.8 +/- 4.4 Ma; the monzonite of the main phase yields a Ar-40/Ar-39 age of 160.7 +/- 3.9 Ma, and the shoshonite basalt of the lower unit of the Kailas Formation yields a Ar-40/Ar-39 age of 161.5 +/- 1.7 Ma. The leading petrogenetic mechanism for the Akatui volcano-plutonic association is crystal fractional differentiation of melts with minor crustal contamination, which can be suggested from the mineralogical and petrographic features and geochemical and isotope characteristics of rocks. The geochemical data for the Akatui volcano-plutonic association show LILE, LREE, U, Th, and Pb enrichment with a characteristic depletion in high-field strength elements (HFSE), such as Nb and Ti. They are also depleted in P. Sr-Nd isotope data (Sr-87/Sr-86((160 Ma)) = 0.70642-0.70688 and epsilon(Nd(160 Ma)) = -0.6 to -2.2) suggest an EMII-type mantle source and could also indicate a negligible degree of crustal contamination in the evolved melts. (C) 2016, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.

Geological and geochemical data indicate that the formation of the granulite-like rocks in the contact aureole of the Yurchik gabbronorite intrusion of the Ganal Range, Kamchatka, was caused by the contact metamorphism, metasomatism, and local melting of the initial volcanosedimentary rocks of the Vakhtalka Sequence of the Ganal Group. The temperature in the inner part of the aureole reached 700–800°C and caused the transformation of the basic volcanic rocks of the sequence into two pyroxene-plagioclase, clinopyroxene-amphibole-plagioclase, and amphibole-plagioclase hornfelses, while sedimentary rocks were converted into garnet-biotite ± cordierite hornfelses. The hornfelsed basic volcanic rocks were locally subjected to metasomatic alteration and magmatic replacement with formation of biotite-orthopyroxene-plagioclase metasomatic bodies containing biotite-orthopyroxene-plagioclase ± garnet veinlets and aggregates. During these processes, sedimentary interlayers were converted into garnet enderbites at 700–800°C and 3.2–4.8 kbar. The comparison of the chemical composition of basic volcanic rocks of the Vakhtalka Sequence and their transformation products indicates that the metasomatic alteration and magmatic replacement correspond to siliceous-alkaline metasomatism (granitization) and cause subsequent and uneven influx of SiO2, Al2O3, Na2O, K2O, Rb, Ba, Zr, Nb, and Cl and removal of Fe, Mg, Mn, Ca, Cr, Co, Ti, Y, and S. REE data on basic metavolcanic rocks, hornfelses, and metasomatites suggest that the processes of hornfelsation, metasomatism, and magmatic replacement of the initial volcanic rocks were accompanied by significant increase in LREE and slight decrease in HREE. The Sr and Nd isotope study of the rocks in the aureole showed that the initial basic volcanic rocks of the Vakhtalka Sequence are isotopically close to both mature island arc tholeiites and mid-ocean ridge basalts. The metasomatic alteration and magmatic replacement of volcanic rocks in the aureole lead to the decrease of 143Nd/144Nd and increase of 87Sr/86Sr approximately parallel to mantle array. Pb isotopic ratios in the studied rocks become more radiogenic from initial metavolcanic rocks to metasomatites.

Metamorphic units of the Khavyven Highland that crop out in the northern portion of the Khavyven Uplift of the basement structures of the Central Kamchatka Trough are formed by rocks of the Khavyven Formation, which are metamorphosed in the green-schist facies. The formation comprises two strata: the lower part that consists of amphibole-micaceous ± garnet, epidote-micaceous ± garnet crystalline schists, and micaceous ± garnet quartzite schists has a total thickness of some 500 m, and the upper part, which is formed by epidote-amphibole and phengite-amphibole green schists and overlying epidote-amphibole-micaceous quartzites, with a visible thickness of some 750 m. The isotopic ratios of Sr, Nd, and Pb were determined in the examined rocks of the Khavyven Formation for the first time. The high 87Sr/86Sr and low 143Nd/144Nd ratios and the high K/La, Ba/Th, Th/Ta, and La/Nb ratios in combination with a deep Ta-Nb minimum indicate that the original volcanites of the crystalline schists of the lower rock mass had a subduction nature. The green schist of the upper rock mass, whose composition corresponds to that of spilitic basalts, have elevated 87Sr/86Sr and 143Nd/144Nd ratios, thus combining indications of depleted melts of the N-MORB and E-MORB types and those of subduction melts, which explains the deep Ta-Nb minimum and the low (La/Yb) N ratios. The isotopic signatures of lead in rocks of the lower and the upper strata are similar. The composition points of the crystalline schists and the green schists are located near the trend of isotopic evolution of lead in the depleted mantle, which indicates that the rocks are closely related to this mantle source.

To study the factors affecting the regioselectivity of the Heck's arylation, several olefins were tested in which the substituents had different electron and steric characteristics. It was found that the type of aryl addition to a sterically unhindered olefin barely depends on the location of effective charges at the carbon atoms of the vinyl group, although it does depend on the LUMO coefficients of the atomic orbitals on the carbon atoms of an olefin. This fact points to the orbital control of the reaction. It was shown that regiospecific formation of alpha-products from 2-monosubstituted and 2,3-disubstituted 1-vinylpyrroles is stipulated by steric factors.

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