Abstract 1,2‐Disubstituted imidazoles react with phosphorus(III) halides in pyridine regioselectively at position 5. The reaction proceeds the more readily, higher electron‐donating ability of 2‐substituent starting imidazole. Hitherto unknown dihalo(imidazol‐5‐yl)phosphines have been obtained, and their properties studied. Also synthetic methods for preparation various monohalo(organyl)(imidazolyl)phosphines developed. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:289–308, 2009;...

Abstract 4‐Selenophosphoryl‐1,2‐disubstituted imidazoles have been obtained by thermal decomposition of methyl 5‐(diamidoselenophosphoryl)imidazolium chlorides. The position selenophosphoryl group in the imidazole ring was proved 1 H, 13 C NMR spectroscopy, and X‐ray analysis. Previously unknown diamido‐ dichloro(imidazol‐4‐yl)‐ phosphonites were synthesized, differences their reactivity compared to analogous 5‐phosphorylated are shown. © 2010 Wiley Periodicals, Inc. Heteroatom Chem...

Abstract A series of fluoropyridines featuring a N,N,N’ ‐trimethyl, N’ ‐trimethylsilylaminal group were subjected to methanolysis. The methanolysis carried out at room temperature yielded mixture products. aminal was transformed into methylimine and ensuing dimethylamine substituted (or not) fluorine atom. relative content pyridine methylimines with dimethylamino without it determined for all fluoropyridines. Additionally, these compounds hydrolyzed aldehydes. This work presents novel...

It has been experimentally proven that the reaction of 1- or 1,2-disubstituted imidazoles with diorganylphosphorus(III) halides proceeds via initial formation N-phosporylated imidazolium salts. Treatment these salts strong bases results in phosphorylation parent at 2- 5-positions, correspondingly. In a previous case, imidazol-2-ylidenes are formed as intermediates. With both N1 and N3 atoms bearing sterically demanding or/and π-donating groups, deprotonation 1,3-disubstituted NaN(SiMe(3))(2)...

Dinuclear silver(I) complexes with bridging N-phosphorylated azolylidene ligands have been synthesized. Subsequent transfer of the to other group 11 metal centers (Cu, Au) has accomplished, highlighting usefulness silver as an easy handle, air- and moisture-stable source these ligands. Preliminary results indicate that dinuclear copper(I) imidazolylidene display notable catalytic efficiency in nitrene reactions.

N-Phosphanyl-N-heterocyclic carbenes (NHCPs) featuring a saturated imidazolin-2-ylidene or tetrahydropyrimid-2-ylidene ring have been synthesized and characterized. The free exhibit good stability can be stored in the solid state for months at ambient temperature without decomposition. Contrary to imidazoline-based NHCPs, which decompose by opening, N-phosphanyltetrahydropyrimid-2-ylidenes isomerize 2-phosphanyl tetrahydropyrimidines upon heating. are capable of acting as chelating ligands...

Synthetic routes to novel N-phosphorylated 1,2,4-triazolium salts have been developed. Treatment of the specified with strong base produces new stable 1,2,4-triazol-5-ylidenes, which add Se in two stages (first at carbene carbon and then phosphorus) rearrange C-phosphorylated triazoles heating. The capacity such triazol-5-ylidenes act as bidentate ligands toward transition-metal centers has also demonstrated; particular, formation dinuclear silver complexes is described herein. structures...

Complexes of palladium(II) with newly disclosed, N-phosphanyl acyclic diaminocarbene ligands are synthesized for the first time and structurally characterized. The coordinate in a chelating fashion, yielding remarkably stable complexes which can be stored without special precautions solid state. Related an isomerized ligand, formed upon 1,2-migration phosphanyl group from nitrogen to adjacent carbon atom, have also been isolated some instances efficiently act as precatalysts Suzuki coupling...

Abstract Three original approaches to the synthesis of N ‐alkyl‐ ′‐phosphanylbenzimidazolium salts, which are precursors corresponding carbenes, were developed. New stable ′‐phosphanylbenzimidazol‐2‐ylidenes prepared in good yields. X‐ray analysis a carbene was made and chemical properties carbenes studied. The reactions with O‐, N‐, C‐nucleophiles found proceed or without cleavage P–N bond. Thermal rearrangement afforded 2‐phosphorylated benzimidazoles.

The first annelated bis- and mono-3H-1,3-azaphosphole ferrocene sandwich compounds have been synthesized from aminoferrocenes, their X-ray structures are compared to those of selenide-protected P═Se analogues, showing net discrepancies both in metallocene backbone conformation fused-ring planarity.

Abstract The phosphorylation reaction of 5–arylmethylidene–1–morpholinocyclopentenes with various phosphorus (III) and (V) halides was studied. It shown that the enamines react giving stable halo– dihalophosphines which are key substances for further synthesis. Hydrolysis phosphorylated does not afford expected ketones, decomposition being observed in acidic media.

Abstract It was found that phosphinimidic isocyanates based on 3‐, 4‐, and 5‐aminopyrazoles could undergo intramolecular heterocyclization to yield previously unknown pyrazolo[1,3,2]diazaphosphorin‐4‐ones containing an endocyclic PN double bond. shown isocyanate 4‐aminopyrazole, in which there are two positions (3 5) available for the cyclization, reacts exclusively at 5‐carbon atom. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:210–215, 2012; View this article online...

Abstract The deprotonation of N ‐di‐ tert ‐butylphosphanyl‐ ‐aryl‐ N′ ‐diisopropylformamidinium salts led to a new type stable acyclic ‐phosphanyl‐diaminocarbene (PADC). Carbenes 8a – 8d were separated as single compounds. molecular structure 8c was determined by X‐ray diffraction analysis. PADC 8 possess an optimal substitution pattern at the nitrogen atoms, and N–C carbene –N bond angle is 120.7°. Structural changes near carbenic carbon atom, such phenyl with mesityl, phosphanyl...

A small library of dinuclear gold(I) complexes with the title ligands has been prepared, encompassing neutral, mono- and dicationic complexes. The luminescence properties in solid state have evaluated, it turns out that neutral monocationic not presenting a rigid metallamacrocyclic structure can exhibit rather strong emissions extend towards red region visible spectrum. vitro anticancer activity also preliminarly evaluated; cytotoxicity seems to correlate complex lipophilicity, whereas...

Using DFT and ab initio calculations, we demonstrate that noncyclic formamidines can undergo thermal rearrangement into their isomeric aminocarbenes under rather mild conditions. We synthesized the silylformamidine, for which lowest activation energy in this process was predicted. Experimental studies proved it to serve as a very reactive nucleophilic carbene. The reactions with acetylenes, benzenes, trifluoromethane proceeded via insertion sp, sp2, sp3 CH bonds. carbene also reacted...

Silylformamidine 1 exists in equilibrium with its carbenic form 1′ due to an easy migration of the silyl group. The reaction variously substituted fluorobenzenes proceeds as insertion nucleophilic carbene into most acidic C–H bond upon mixing reagents and does not require any catalyst. According DFT calculations, classical interpretation proceeding via a three-membered transition state structure requires high activation energy. Instead, low barriers are predicted for transfer proton aromatic...

A novel two-step method for formylation of fluoropyridines with silylformamidine Me3 SiC(=NMe)NMe2 (1) under catalyst-free conditions was developed. series all possible 18 featuring one to four fluorine atoms were subjected the reaction 1 existing in equilibrium its carbenic form Me2 NC(:)N(Me)SiMe3 (1'). Among them, 12 shown react via C-H insertion. The proceeded either at β- or γ-positions affording corresponding aminals. more pyridines, easier proceeded. We also hypothesized that...

Abstract We studied the reaction of N ‐alkyl(aryl)pyrazoles with silylformamidine 1 that exists in an equilibrium its carbene form via migration trimethylsilyl group from carbon to nitrogen atom. The insertion proceeded at C−H 5 th position. featuring substituents such as Br, CN and NO 2 reacted readily affording corresponding aminals. This approach allowed us synthesize pyrazole dialdehyde phosphine a vicinal aldehyde group. does not require any catalyst. position was unambiguously...

The representative of P,P,P-trichloroylides5-methyl-2-phenyl-4-(trichlorophosphoranylidene)-2,4-dihydro-3H-pyrazol-3-onewas synthesized. Its constitution was confirmed by 1H, 13C, and 31P NMR spectroscopy X-ray analysis. Some chemical properties were studied compared with ones P,P,P-trimethylylide5-methyl-2-phenyl-4-(trimethylphosphoranylidene)-2,4-dihydro-3H-pyrazol-3-one. DFT calculations the model molecules carried out.