Center for Magnetic Resonance

M.T. Dau, J.R. Shakirova, A.J. Karttunen, E.V. Grachova, S.P. Tunik, A.S. Melnikov, T.A. Pakkanen, I.O. Koshevoy

“Coinage Metal Complexes Supported by the Tri- and Tetraphosphine Ligands”

Inorg. Chem., 2014, ASAP

DOI: 10.1021/ic500402m

A series of tri- and tetranuclear phosphine complexes of d10 metal ions supported by the polydentate ligands, bis(diphenylphosphinomethyl)phenylphosphine (PPP) and tris(diphenylphosphinomethyl)phosphine (PPPP), were synthesized. All the compounds under study, [AuM2(PPP)2]3+ (M = Au (1), Cu (2), Ag (3)), [M4(PPPP)2]4+ (M = Ag (4), Au (5)), [AuAg3(PPPP)2]4+ (6), and [Au2Cu2(PPPP)2(NCMe)4]4+ (7), were characterized crystallographically. The trinuclear clusters 1–3 contain a linear metal core, while in the isostructural tetranuclear complexes 4–6 the metal framework has a plane star-shaped arrangement. Cluster 7 adopts a structural motif that involves a digold unit bridged by two arms of the PPPP phosphines and decorated two spatially separated CuI ions chelated by the remaining P donors. The NMR spectroscopic investigation in DMSO solution revealed the heterometallic clusters 2, 3, and 6 are stereochemically nonrigid and undergo reversible metal ions redistribution between several species, accompanied by their solvation–desolvation. The complexes 1–3 and 5–7 exhibit room temperature luminescence in the solid state (Φem = 6–64%) in the spectral region from 450 to 563 nm. The phosphorescence observed originates from the triplet excited states, determined by the metal cluster-centered dσ* → pσ transitions.

A.P. Molchanov, R.S. Savinkov, A.V. Stepakov, G.L. Starova, R.R. Kostikov, V.S. Barnakova, A.V. Ivanov

“A Highly Efficient and Stereoselective Cycloaddition of Nitrones to N-Vinylpyrroles”

Synthesis, 2014, 46, 0771-0780

DOI: 10.1055/s-0033-1340479

1,3-Dipolar cycloadditions of a number of C-aryl, C-carbamoyl-, and C,C-bis(methoxycarbonyl)nitrones and substituted N-vinylpyrroles proceed with high efficiency and regioselectivity with the formation of only one isomeric substituted 5-(1H-pyrrol-1-yl)isoxazolidine cycloadduct.
 

 
A.V. Stepakov, A.G. Larina, V.M. Boitsov, V.V. Gurzhiy, A.P. Molchanov, R.R. Kostikov

“Synthesis of indene derivatives via reactions of vinylidenecyclopropanes with the N-acyliminium cations generated from hydroxylactams”

Tetrahedron Lett., 2014, 55, 2022-2026

DOI: 10.1016/j.tetlet.2014.02.039

A novel route for the synthesis of 1H-indene derivatives via the reactions of vinylidenecyclopropanes (VCPs) with the N-acyliminium cations generated from hydroxylactams is described.

Alena S. Pankova, Mikhail A. Kuznetsov

“Synthesis and thermal transformations of spiro-fused N-phthalimidoaziridines”

Tetrahedron Letters, 2014, In Press

DOI: 10.1016/j.tetlet.2014.03.014

Oxidation of N-aminophthalimide in the presence of 2-arylideneinden-1,3-diones with electron-withdrawing substituents gives the corresponding 3-aryl-1-phthalimidospiro[aziridine-2,2’-indene]-1’,3’-diones in good yields. Heating these aziridines with standard dipolarophiles (N-phenylmaleimide, dimethyl acetylenedicarboxylate, maleate and fumarate) leads, in most cases, to spiro[inden-2,2’-pyrrole] derivatives as products of 1,3-dipolar cycloaddition of the intermediate azomethine ylides with up to 70-95% yields in the case of N-phenylmaleimide. As is typical for 2-acylaziridines, the competing rearrangement into 2-aryl-4H-indeno[2,1-d][1,3]oxazol-4-ones prevails for less active dipolarophiles. Increasing the electron-releasing properties of the 3-aryl ring allows the observation of the push-pull effect of electron-donating and electron-withdrawing substituents on the ease of the three-membered ring-opening.

M. A. Kuznetsov, A. Ya. Bespalov

“One-pot, Three-component Synthesis of [1,3]thiazolo[4,3-b][1,3,4]thiadiazoles: Correct Structure of the Products”

Chem. Heterocycl. Compd., 2014, 49, 1458-1463

DOI: 10.1007/s10593-014-1396-4

The products of the one-pot, three-component synthesis of [1,3]thiazolo-[4,3-b][1, 3, 4]thiadiazoles from aromatic aldehydes, thioglycolic acid, and compounds containing a C(=S)–N–NH2 fragment (thiosemicarbazide or 4-amino-2,4-dihydro-3H-1,2,4-triazole-3-thiones) are not condensed hetero-cycles (as reported by several researchers), but are thiosemicarbazones or triazolylimines of the aldehydes used.

Julia R. Shakirova, Elena V. Grachova, Antti J. Karttunen, Vladislav V. Gurzhiy, Sergey P. Tunik and Igor O. Koshevoy

“Metallophilicity-assisted assembly of phosphine-based cage molecules”

Dalton Trans., 2014, Advance Article

DOI: 10.1039/c3dt53645a

A family of supramolecular cage molecules has been obtained via self-assembly of the phosphine–gold coordination complexes following an aurophilicity-driven aggregation approach. Use of the di- (PP) or tridentate (PPP) phosphine ligands P_n (n = 2, 3) with rigid polyaromatic backbones leads to clean formation of the coordination P_n(Au(tht))_nⁿ⁺ species, sequential treatment of which with H₂O/NEt₃ and excess of H₂NBu^t gives the finite 3D structures of two major types. The cylindrical-like hexametallic cages [(PPAu₂)₃(μ₃-NBu^t)₂]²⁺ are based on the diphosphines PP = 1,4-bis(diphenylphosphino)benzene (1), 4,4′-bis(diphenylphosphino)biphenyl (2), 4,4′′-bis(diphenylphosphino)terphenyl (3), while the triphosphine PPP (1,3,5-tris(diphenylphosphinophenyl)benzene) produces a tetrahedral dodecagold complex [(PPPAu₃)₄(μ₃-NBu^t)₄]⁴⁺ (4). The cages 1–4 have been studied using the ESI-MS and ¹H, ³¹P NMR spectroscopy, and the crystal structures of 1 and 4 were determined by an X-ray diffraction study. The NMR spectroscopic investigations showed that cylindrical complexes 1–3 undergo twisting-like interconversion of the helical P↔M isomers in solution, while 4 is a stereochemically rigid compound retaining its axially chiral architecture. The difference in dynamic behaviour was rationalized using computational studies with density functional methods.

Ilya S. Krytchankou, Dmitry V. Krupenya, Antti J. Karttunen, Sergey P. Tunik, Tapani A. Pakkanen, Pi-Tai Choud, Igor O. Koshevoy
“Triphosphine-supported bimetallic Au^I–M^I (M = Ag, Cu) alkynyl clusters”
Dalton Trans., 2014, Advance Article
DOI: 10.1039/C3DT52658E

The luminescent bimetallic aggregates reversibly undergo dissociation or isomerization in solution and exhibit photoemission in the solid state (414 to 566 nm).

D. V. Krupenya, P. A. Snegurov, E. V. Grachova, V. V. Gurzhiy, S. P. Tunik, A. S. Melnikov, P. Yu. Serdobintsev, E. G. Vlakh, E. S. Sinitsyna, and T. B. Tennikova

New Supramolecular Au^I−Cu^I Complex as Potential Luminescent
Label for Proteins

Inorganic Chemistry 2013

Aleksey L. Mindich, Nadezhda A. Bokach, Maxim L. Kuznetsov, Galina L. Starova, Andrey P. Zhdanov, Konstantin Yu. Zhizhin, Serguei A. Miltsov, Nikolay T. Kuznetsov, and Vadim Yu. Kukushkin

“Borylated Tetrazoles from Cycloaddition of Azide Anions to Nitrilium Derivatives of closo-Decaborate Clusters”

Organometallics 2013

Dmitrii S. Bolotin, Nadezhda A. Bokach, Andreii S. Kritchenkov, Matti Haukka, and Vadim Yu. Kukushkin

“Amidrazone Complexes from a Cascade Platinum(II)-Mediated Reaction between Amidoximes and Dialkylcyanamides”

Inorganic Chemistry 2013

Nikolai V. Rostovskii, Mikhail S. Novikov, Alexander F. Khlebnikov, Sergei M. Korneev and Dmitry S. Yufit

“Cu(II)-catalyzed domino reaction of 2H-azirines with diazotetramic and diazotetronic acids. Synthesis of 2-substituted 2H-1,2,3-triazoles”

Org. Biomol. Chem., 2013, 11, 5535

DOI

Julia R. Shakirova, Elena V. Grachova, Alexei S. Melnikov, Vladislav V. Gurzhiy, Sergey P. Tunik, Matti Haukka, Tapani A. Pakkanen, and Igor O. Koshevoy

“Toward Luminescence Vapochromism of Tetranuclear AuI–CuI Clusters”

Organometallics 2013, 32 (15), 4061.

Abstracts