Volcano–Plutonic Complex of the Tumrok Range (Eastern Kamchatka): An Example of the Ural-Alaskan Type Intrusion and Related Volcanic Series

Zoned plutons, composed of dunites, pyroxenites, and gabbroic rocks, have been referred to as the Ural-Alaskan type complexes (UA-complexes) and occur in numerous paleo-arc settings worldwide. Many of these complexes are source rocks for economic placers of platinum-group metals. Thus, it is important to understand how UA-complexes form and the origin and behavior of platinum-group elements (PGEs). It is widely assumed that the UA-complexes result from differentiation of supra-subduction high-Ca high-Mg sub-alkaline magmas. However, there is a lack of direct evidence for the existence and differentiation of such magmas, mainly because cases of UA-complexes being spatially and temporally linked to co-genetic volcanics are unknown. We studied an UA-complex from the Tumrok range (Eastern Kamchatka) where a dunite-clinopyroxenite-gabbro assemblage is spatially and temporary related to high-Ca volcanics (i.e., picrites and basalts). Based on the mineral and chemical composition of the rocks, mineral chemistry, and composition of melt inclusions hosted within rock-forming minerals, we conclude that the intrusive assemblage and the volcanics are co-genetic and share the same parental magma of ankaramitic composition. Furthermore, the compositions of the plutonic rocks are typical of UA-complexes worldwide. Finally, the rocks studied exhibit a full differentiation sequence from olivine-only liquidus in picrites and dunites to eutectic crystallization of diopside or hornblende, plagioclase, and K-Na feldspar in plagio-wehrlites and gabbroic rocks. All these results make the considered volcano–plutonic complex a promising case for petrological studies and modelling of UA-complex formation

Synthesis of 3-(Pyridin-2-yl)quinazolin-2,4(1<i>H,</i>3<i>H</i>)-diones via Annulation of Anthranilic Esters with <i>N</i>-pyridyl Ureas

A new route for the synthesis of quinazolin-2,4(1H,3H)-diones and thieno [2,3-d]pyrimidine-2,4(1H,3H)-diones substituted by pyridyl/quinolinyl moiety in position 3 has been developed. The proposed method concluded in an annulation of substituted anthranilic esters or 2-aminothiophene-3-carboxylates with 1,1-dimethyl-3-(pyridin-2-yl) ureas. The process consists of the formation of N-aryl-N′-pyridyl ureas followed by their cyclocondensation into the corresponding fused heterocycles. The reaction does not require the use of metal catalysts and proceeds with moderate to good yields (up to 89%). The scope of the method is more than 30 examples, including compounds with both electron-withdrawing and electron-donating groups, as well as diverse functionalities. At the same time, strong electron-acceptor substituents in the pyridine ring of the starting ureas reduce the product yield or even prevent the cyclocondensation step. The reaction can be easily scaled to gram quantities

Hybrid 2D Supramolecular Organic Frameworks (SOFs) Assembled by the Cooperative Action of Hydrogen and Halogen Bonding and π⋯π Stacking Interactions

The cis- and trans-isomers of 6-(3-(3,4-dichlorophenyl)-1,2,4-oxadiazol-5-yl)cyclohex-3-ene-1-carboxylic acid (cis-A and trans-A) were obtained by the reaction of 3,4-dichloro-N′-hydroxybenzimidamide and cis-1,2,3,6-tetrahydrophthalic anhydride. Cocrystals of cis-A with appropriate solvents (cis-A‧½(1,2-DCE), cis-A‧½(1,2-DBE), and cis-A‧½C6H14) were grown from 1,2-dichloroethane (1,2-DCE), 1,2-dibromoethane (1,2-DBE), and a n-hexane/CHCl3 mixture and then characterized by X-ray crystallography. In their structures, cis-A is self-assembled to give a hybrid 2D supramolecular organic framework (SOF) formed by the cooperative action of O–H⋯O hydrogen bonding, Cl⋯O halogen bonding, and π⋯π stacking. The self-assembled cis-A divides the space between the 2D SOF layers into infinite hollow tunnels incorporating solvent molecules. The energy contribution of each noncovalent interaction to the occurrence of the 2D SOF was verified by several theoretical approaches, including MEP and combined QTAIM and NCIplot analyses. The consideration of the theoretical data proved that hydrogen bonding (approx. −15.2 kcal/mol) is the most important interaction, followed by π⋯π stacking (approx. −11.1 kcal/mol); meanwhile, the contribution of halogen bonding (approx. −3.6 kcal/mol) is the smallest among these interactions. The structure of the isomeric compound trans-A does not exhibit a 2D SOF architecture. It is assembled by the combined action of hydrogen bonding and π⋯π stacking, without the involvement of halogen bonds. A comparison of the cis-A structures with that of trans-A indicated that halogen bonding, although it has the lowest energy in cis-A-based cocrystals, plays a significant role in the crystal design of the hybrid 2D SOF. The majority of the reported porous halogen-bonded organic frameworks were assembled via iodine and bromine-based contacts, while chlorine-based systems—which, in our case, are structure-directing—were unknown before this study

Conformation-Associated C···<i>d_z</i>²-Pt^II Tetrel Bonding: The Case of Cyclometallated Platinum(II) Complex with 4-Cyanopyridyl Urea Ligand

The nucleophilic addition of 3-(4-cyanopyridin-2-yl)-1,1-dimethylurea (1) to cis-[Pt(CNXyl)2Cl2] (2) gave a new cyclometallated compound 3. It was characterized by NMR spectroscopy (1H, 13C, 195Pt) and high-resolution mass spectrometry, as well as crystallized to obtain two crystalline forms (3 and 3·2MeCN), whose structures were determined by X-ray diffraction. In the crystalline structure of 3, two conformers (3A and 3B) were identified, while the structure 3·2MeCN had only one conformer 3A. The conformers differed by orientation of the N,N-dimethylcarbamoyl moiety relative to the metallacycle plane. In both crystals 3 and 3·2MeCN, the molecules of the Pt(II) complex are associated into supramolecular dimers, either {3A}2 or {3B}2, via stacking interactions between the planes of two metal centers, which are additionally supported by hydrogen bonding. The theoretical consideration, utilizing a number of computational approaches, demonstrates that the C···dz2(Pt) interaction makes a significant contribution in the total stacking forces in the geometrically optimized dimer [3A]2 and reveals the dz2(Pt)→π*(PyCN) charge transfer (CT). The presence of such CT process allowed for marking the C···Pt contact as a new example of a rare studied phenomenon, namely, tetrel bonding, in which the metal site acts as a Lewis base (an acceptor of noncovalent interaction)

Stacking Interactions: A Supramolecular Approach to Upgrade Weak Halogen Bond Donors

The co-crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co-crystals TCB center dot ArX (ArX=PhCl, PhBr, 4-MeC6H4Cl, 4-MeC6H4Br, 4-MeOC6H4Cl, 1,2-Br2C6H4) which were studied by X-ray diffraction. In these systems, the strong collective effect of pi center dot center dot center dot pi stacking interactions and lone pair-(X)center dot center dot center dot pi-hole-(C) bondings between TCB and ArX promote the strength of X center dot center dot center dot N-cyano halogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the o-hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the sigma- hole-(Cl) value (1.5 kcal/mol) in the haloarene 4-MeOC6H4Cl (featuring an electron-rich arene moiety and exhibiting very poor sigma-hole-(CI) ability) increases significantly in the stacked trimer (TCB)(2)center dot 4-MeOC6H4Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X center dot center dot center dot N-cyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes

Volcano–Plutonic Complex of the Tumrok Range (Eastern Kamchatka): An Example of the Ural-Alaskan Type Intrusion and Related Volcanic Series

Zoned plutons, composed of dunites, pyroxenites, and gabbroic rocks, have been referred to as the Ural-Alaskan type complexes (UA-complexes) and occur in numerous paleo-arc settings worldwide. Many of these complexes are source rocks for economic placers of platinum-group metals. Thus, it is important to understand how UA-complexes form and the origin and behavior of platinum-group elements (PGEs). It is widely assumed that the UA-complexes result from differentiation of supra-subduction high-Ca high-Mg sub-alkaline magmas. However, there is a lack of direct evidence for the existence and differentiation of such magmas, mainly because cases of UA-complexes being spatially and temporally linked to co-genetic volcanics are unknown. We studied an UA-complex from the Tumrok range (Eastern Kamchatka) where a dunite-clinopyroxenite-gabbro assemblage is spatially and temporary related to high-Ca volcanics (i.e., picrites and basalts). Based on the mineral and chemical composition of the rocks, mineral chemistry, and composition of melt inclusions hosted within rock-forming minerals, we conclude that the intrusive assemblage and the volcanics are co-genetic and share the same parental magma of ankaramitic composition. Furthermore, the compositions of the plutonic rocks are typical of UA-complexes worldwide. Finally, the rocks studied exhibit a full differentiation sequence from olivine-only liquidus in picrites and dunites to eutectic crystallization of diopside or hornblende, plagioclase, and K-Na feldspar in plagio-wehrlites and gabbroic rocks. All these results make the considered volcano–plutonic complex a promising case for petrological studies and modelling of UA-complex formation

Palladium(II) and Platinum(II) Deprotonated Diaminocarbene Complexes Based on N-(2-Pyridyl)ureas with Oxadiazole Periphery

Metal mediated coupling of isocyanides with substituted N-(pyridine-2-yl) ureas was first used to incorporate privileged biological motifs into platinum metal complexes. We synthesized two palladium(II) and two platinum(II) cyclometallated species with oxadiazole cores. The compounds were isolated in good yields (61&ndash;73%) and characterized by high-resolution mass spectrometry and 1H, 13C, and 195Pt NMR spectroscopies. The structures of three complexes were additionally elucidated by X-ray diffraction analysis. These complexes indeed showed cytotoxic activity. The species bearing the 1,3,4-oxadiazole moiety exhibit more potency than the ones with the 1,2,4-oxadiazole ring. Particularly, the cytotoxic effect of both 1,3,4-oxadiazole-based complexes towards T98G cells significantly exceeds the common antitumor metal-drug cisplatin

Palladium(II) and Platinum(II) Deprotonated Diaminocarbene Complexes Based on <i>N</i>-(2-Pyridyl)ureas with Oxadiazole Periphery

Metal mediated coupling of isocyanides with substituted N-(pyridine-2-yl) ureas was first used to incorporate privileged biological motifs into platinum metal complexes. We synthesized two palladium(II) and two platinum(II) cyclometallated species with oxadiazole cores. The compounds were isolated in good yields (61–73%) and characterized by high-resolution mass spectrometry and 1H, 13C, and 195Pt NMR spectroscopies. The structures of three complexes were additionally elucidated by X-ray diffraction analysis. These complexes indeed showed cytotoxic activity. The species bearing the 1,3,4-oxadiazole moiety exhibit more potency than the ones with the 1,2,4-oxadiazole ring. Particularly, the cytotoxic effect of both 1,3,4-oxadiazole-based complexes towards T98G cells significantly exceeds the common antitumor metal-drug cisplatin

Noncovalent Chelation by Halogen Bonding in the Design of Metal-Containing Arrays: Assembly of Double σ‑Hole Donating Halolium with Cu^I‑Containing O,O‑Donors

Five new copper(I) complexescomposed of the paired dibenzohalolium and [CuL2]− (L = 1,2,4-oxadiazolate) counterions in which O,O-atoms of the anion are simultaneously linked to the halogen atomwere generated and isolated as the solid via the three-component reaction between [Cu(MeCN)4](BF4), sodium 1,2,4-oxadiazolates, and dibenzohalolium triflates (or trifluoroacetates). This reaction is different from the previously reported CuI-catalyzed arylation of 1,2,4-oxadiazolones by diaryliodonium salts. Inspection of the solid-state X-ray structures of the complexes revealed the strong three-center X···O,O (X = Br, I) halogen bonding occurred between the oxadiazolate moieties and dibenzohalolium cation. According to performed theoretical calculations, this noncovalent interaction (or noncovalent chelation) was recognized as the main force in the stabilization of the copper(I) complexes. An explanation for the different behavior of complexes, which provide either chelate or nonchelate binding, is based on the occurrence of additional −CH3···π interactions, which were also quantified