- Synthesis of first representatives of 46-membered P,N,O-containing cyclophanes and their transition metal complexes
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A condensation of phenyl- or l-menthylphosphine with formaldehyde and 4,4′-bis-(4′-aminophenoxy)biphenyl proceeding as a covalent self-assembly gave rise to the first representatives of 46-membered P,N,O-containing cyclophanes, namely, 13,17,83,87-tetra-R-3,6,10,13-tetraoxa-1,8(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,5,7,9,11,12,14(1,4)-octabenzenacyclotetradecaphanes (R = Ph (1), l-Ment (2)). The cage macrocyclic tetraphosphine 2 reacted with (cyclooctadiene)dichloroplatinum(ii) and -palladium(ii), as well as with (tetrahydrofuran)pentacarbonyltungsten(0) with the formation of binuclear complexes, in which the metal atoms are coordinated to 1,5-diaza-3,7-diphosphacyclooctane fragments by the P,P-chelate mode.
- Nikolaeva, Yu. A.,Balueva,Ignat'eva,Musina,Karasik
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- New aminomethylphosphines with cyanophenyl substituents at the nitrogen atoms
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A condensation of bis(hydroxymethyl)arylphosphines with 3- and 4-aminobenzonitriles leads to the corresponding 3,7-diaryl-1,5-bis(cyanophenyl)- 1,5-diaza-3,7-diphosphacyclooctanes. Acyclic (aryl)bis[N-(2-cyanophenyl) aminomethyl]phosphines are formed in the case of 2-aminobenzonitrile. Molecular and crystalline structure of the compounds obtained was studied by X-ray diffraction analysis.
- Spiridonova,Balueva,Krivolapov,Litvinov,Musina,Karasik,Sinyashin
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- Synthesis of aminomethylphosphines with triazaadamantane fragments
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The reaction of (hydroxymethyl)diphenylphosphine with 7-amino-1,3,5-triazaadamantane, followed by ready oxidation of the initially formed aminomethylphosphine gave diphenyl[(1,3,5-triazaadamantan-7-yl)aminomethyl]phosphine oxide. The reactions of bis(hydr
- Kuznetsov,Balueva,Serova,Nikonov
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- Process for preparation of phosphorane and phosphonyl compounds
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The invention relates to the field of new materials of fine chemicals, in particular to a new safe, convenient, mild, efficient, environment-friendly and economical preparation process technology of phosphorane and phosphonyl compounds.
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- Catalyst Pendent-Base Effects on Cyclization of Alkynyl Amines
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A family of [CpRu(PP)(MeCN)]PF6 complexes (2 a–e and 4) were prepared in which the bis-phosphine ligand contains a pendent tertiary amine in the second-coordination sphere. 2 a–e contain PPh2NR′2 ligands with two amine groups as the pendent base. Complex 4 has the PPh2NPh1 ligand with only one pendent amine. The catalytic performance of 2 a–e and 4 were assessed in the cyclization of 2-ethynyl aniline and 2-ethynylbenzyl alcohol. It was revealed that the positioning of the pendent amine near the metal active site is essential for high catalyst performance. A comparison of PPh2NR′2 catalysts (2 a–e) showed minimal difference in performance as a function of pendent amine basicity. Rather, only a threshold basicity – in which the pendent amine was more basic than the substrate – was required for high performance.
- Stubbs, James M.,Chapple, Devon E.,Boyle, Paul D.,Blacquiere, Johanna M.
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p. 3694 - 3702
(2018/08/06)
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- Synthesis and Structure of N-Pyridyl-Containing Cyclic Aminomethylphosphines
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N-pyridyl-containing cyclic aminomethylphosphines have been prepared via condensation of the corresponding bis(hydroxymethyl)arylphosphines with p-aminopyridine and m-aminomethylpyridine.
- Spiridonova, Yu. S.,Musina,Dayanova,Naumova,Litvinov,Karasik
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p. 2257 - 2262
(2019/01/04)
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- Light-driven hydrogen production from aqueous solutions based on a new Dubois-type nickel catalyst
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In this work, we report a new photocatalytic system that links multifunctional semiconductor nanocrystals with emerging water-soluble molecular catalysts made of earth-abundant elements for H2 generation [Ni(P2RN2R′)2(BF4)2]4-, R = Ph, R′ = [PhSO3]- (NiS). This noble metal free hybrid exhibits remarkable catalytic activity with a turnover number of 511 for H2 production and a photon-to-H2 conversion efficiency of 12.5%. The mechanistic insight into such high efficiency in this photocatalytic system was examined using a combination of steady-state emission and time-resolved absorption spectroscopy.
- Zhou,Yang,Huang
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p. 7471 - 7475
(2017/04/04)
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- Coordination and conformational isomers in mononuclear iron complexes with pertinence to the [FeFe] hydrogenase active site
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A series of six mononuclear iron complexes of the type [Fe(X-bdt)(P R2NPh2)(CO)] (PR 2NPh2 = 1,5-diaza-3,7-diphosphaoctane, bdt = benzenedithiolate with X = H, Cl2 or Me and R = Ph, Bn, Cyc or tert-Bu) was prepared. This new class of penta-coordinate iron complexes contains a free coordination site and a pendant base as essential structural features of the [FeFe]-hydrogenase active site. The bidentate nature of the PR2NPh2 ligands was found to be crucial for the preferential formation of coordinatively unsaturated penta-coordinate complexes, which is supported by first principle calculations. IR-spectroscopic data suggest the presence of coordination isomers around the metal center, as well as multiple possible conformers of the PR 2NPh2 ligand. This finding is further corroborated by X-ray crystallographic and computational studies. 31P{1H}-NMR- and IR-spectroscopic as well as electrochemical measurements show that the electronic properties of the complexes are strongly, and independently, influenced by the P-substituents at the PR2NPh2 ligand as well as by modifications of the bdt bridge. These results illustrate the advantages of this modular platform, which allows independent and selective tuning through site specific modifications. Potential catalytic intermediates, namely singly reduced and protonated complexes, have been further investigated by spectroscopic methods and exhibit remarkable stability. Finally, their general capacity for electro-catalytic reduction of protons to molecular hydrogen was verified.
- Orthaber, Andreas,Karnahl, Michael,Tschierlei, Stefanie,Streich, Daniel,Stein, Matthias,Ott, Sascha
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p. 4537 - 4549
(2014/03/21)
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- Electrocatalytic oxidation of formate by [Ni(PR 2NR′2)2(CH3CN)] 2+ complexes
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[Ni(PR2NR′2) 2(CH3CN)]2+ complexes with R = Ph, R′ = 4-MeOPh or R = Cy, R′ = Ph, and a mixed-ligand [Ni(PR 2NR′2)(PR′′ 2NR′
- Galan, Brandon R.,Schoeffel, Julia,Linehan, John C.,Seu, Candace,Appel, Aaron M.,Roberts, John A. S.,Helm, Monte L.,Kilgore, Uriah J.,Yang, Jenny Y.,Dubois, Daniel L.,Kubiak, Clifford P.
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experimental part
p. 12767 - 12779
(2011/10/05)
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- Synthesis of novel paracyclophanes with linear P,N-containing spacers
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Condensation of bis(hydroxymethyl)mesityl-and bis(hydroxymethyl) phenylphosphines with N,N′-disubstituted bis(4-aminophenyl)methanes and bis(4-amino-3-carboxyphenyl)methane occurred as covalent self-assembly spontaneously giving a mixture of trans-and cis-diastereomers of 1,5,19,23-tetra-R′-3,21-di-R-1,5,19,23-tetraaza-3,21-diphospha[5.1.5.1] paracyclophanes as the major products. The trans-isomer (R is mesityl; R′ is methyl) was isolated in the individual state and structurally characterized by X-ray diffraction analysis. Sulfurization of macrocyclic diphosphines (R = Ph; R′ is 3-pyridylmethyl or 4-pyridylmethyl) gave the corresponding diphosphine disulfides, the trans-stereoisomer being isolated in the individual state.
- Ignat'eva,Balueva,Karasik,Kulikov,Kozlov,Latypov,Loennecke,Hey-Hawkins,Sinyashin
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p. 1828 - 1837
(2008/09/20)
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- Water-soluble hydroxyalkylated phosphines: Examples of their differing behaviour toward ruthenium and rhodium
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The reaction of P(CH2OH)3 (I) and P(C 6H5)(CH2OH)2 (II) with RuCl 3 in methanol eliminates two equivalents of formaldehyde to yield the mixed tertiary and secondary phosphine com
- Higham, Lee J.,Whittlesey, Michael K.,Wood, Paul T.
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p. 4202 - 4208
(2007/10/03)
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- Self-assembly of novel macrocyclic aminomethylphosphines with hydrophobic intramolecular cavities
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Novel macroheterocyclic tetraphosphines, namely, 1,1′,5,5′- bis(arylene)-bis(1,5-diaza-3,7-diphosphacyclooctanes) 2-6, were obtained without the use of high-dilution techniques or any matrix by the reaction of bis(hydroxymethyl)-organylphosphines with primary aromatic diamines containing two p-phenylene fragments linked by various one-atom bridges in a molecular self-assembly process. The structures of 4, 5 and 6 were investigated by X-ray crystal structure analyses. The macrocyclic cavities can be described as a truncated rhombohedral prism with side faces formed by phenylene rings and 1,5-diaza-3,7-diphosphacyclooctanes in the truncated acute angles. In the crystals of these macrocycles, solvating DMF molecules are present, and a methyl group from each of two DMF molecules penetrates the macrocyclic cavities of 4 and 5 from either side, whereas only one disordered molecule of DMF penetrates the cavity of macrocycle 6. Different types of crystal packing are observed for the P-benzyl-substituted compounds 4 and 5 and for the P-mesityl-substituted compound 6: for 4 and 5 the formation of alternating layers containing the macrocycles and the DMF molecules is observed, in which the cavities of the macrocyclic molecules form channels and the DMF molecules are located in the centers of the channels; in the crystal of 6, six molecules are arranged around the 3 axis in the fashion of a six-bladed propeller.
- Balueva, Anna S.,Kuznetsov, Roman M.,Ignat'eva, Svetlana N.,Karasik, Andrey A.,Gubaidullin, Aidar T.,Litvinov, Igor A.,Sinyashin, Oleg G.,Loennecke, Peter,Hey-Hawkins, Evamarie
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p. 442 - 447
(2007/10/03)
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- Synthesis of new macrocyclic aminomethylphosphines based on 4,4'-diaminodiphenylmethane and its derivatives
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The reaction of bis(hydroxymethyl)phenylphosphine with 4,4'-diaminodiphenylmethane in DMF afforded 1,1',5,5'-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis
- Kuutetsov, R. M.,Balueva, A. S.,Litvinov, I. A.,GubaiduUin, A. T.,Nikonov, G. N.,Karasik, A. A.,Sinyashin, O. G.
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p. 151 - 156
(2007/10/03)
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