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mgr inż. Natalia Szynkiewicz
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total: 23
Catalog Publications
Year 2022
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Activation of the C=P bond in phosphanylphosphaalkenes C=P–P bond system) in the reaction with nucleophilic reagents: MeLi, nBuLi and tBuLi
PublicationThree reactions of phosphanylphosphaalkene (1) with nucleophiles were performed to activate the diphosphorus monomer. We observed similar results in the reactions with MeLi and nBuLi, in which the P–P bond is cleavaged and triphosphorus systems [P(Me)2–CH(biph)–CH(biph)–P–(PtBu 2)]- (1a'') and [P(nBu)2–CH(biph)–CH(biph)–P–(PtBu 2)]- (1b''), respectively, are formed depending on the nucleophilic reagent (biph ¼ biphenyl). In the...
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Exploring the Reactivity of Unsymmetrical Diphosphanes toward Heterocumulenes: Access to Phosphanyl and Phosphoryl Derivatives of Amides, Imines, and Iminoamides
PublicationWe present a comprehensive study on the diphosphanation of iso(thio)cyanates by unsymmetrical diphosphanes. The reactions involving unsymmetrical diphosphanes and phenyl isocyanate or phenyl thioisocyanate gave rise to phosphanyl, phosphoryl, and thiophosphoryl derivatives of amides, imines, and iminoamides. The structures of the diphosphanation products were confirmed through NMR spectroscopy, IR spectroscopy, and single-crystal...
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Monomeric Triphosphinoboranes: Intramolecular Lewis Acid–Base Interactions between Boron and Phosphorus Atoms
PublicationHerein, we present the synthesis of the first fully characterized monomeric triphosphinoboranes. The simple reaction of boron tribromide with three equivalents of bulky lithium phosphide tBu2PLi yielded triphosphinoborane (tBu2P)3B. Triphosphinoboranes with diversified phosphanyl substituents were obtained via a two-step reaction, in which isolable bromodiphosphinoborane (tBu2P)2BBr is first formed and then reacts with one equivalent...
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Phosphinoborinium cation: a synthon for cationic B-P bond systems
PublicationHerein, we report access to phosphinoborinium cations via heterolytic cleavage of the boron-bromide bond in bromophosphinoborane. The product of the reaction was isolated as a dimeric dication possessing a planar P2B2 core. Activation of C-H and C-P bonds in the dication led to formation of the borinium-phosphaborene adduct. Reactivity studies revealed that title cation exhibits ambiphilic properties and intramolecular frustrated...
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Phosphinophosphoranes: Mixed-Valent Phosphorus Compounds with Ambiphilic Properties
PublicationHerein, we present a simple synthesis of mixed-valent phosphinophosphoranes bearing three- and five-coordinate phosphorus centers. Compounds with phosphorus–phosphorus bonds were synthesized via a reaction of lithium phosphides RR′PLi with cat2PCl (cat = catecholate), whereas derivatives with methylene-linked phosphorus centers were obtained via a reaction of phosphanylmethanides RR′CH2Li with cat2PCl. The presence of accessible...
Year 2021
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Diphosphinoboranes as Intramolecular Frustrated Lewis Pairs: P–B–P Bond Systems for the Activation of Dihydrogen, Carbon Dioxide, and Phenyl Isocyanate
PublicationHerein, we present the first example of the activation of small molecules by P-B-P bond systems. The reactivity study involves reactions of two selected diphosphinoboranes, (tBu2P)2BPh (1’) and (Cy2P)2BNiPr2 (2), that differ in terms of their structural and electronic properties for the activation of dihydrogen, carbon dioxide, and phenyl isocyanate. Diphosphinoborane 1’ activates H2 under very mild conditions in the absence of...
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Experimental and theoretical investigation of the reactivity of [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2}] towards selected ketones
PublicationIn this work, we report a new type of reactivity of [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2}] (1) towards ketones (BDI* = 2,6-diisopropylphenyl-β-methyldiketiminate ligand). In the reaction of 1 with acetone, cyclopentanone or cyclohexanone, a ketone moiety is inserted into Ti–Pphosphanyl or Ti–Pphosphido bonds to form complexes with a new C–P–P moiety, providing [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2-C(Me)2O}] (2a), [(BDI*)Ti(Cl){η2-OC(Me)2P(SiMe3)-PiPr2}]...
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Reactivity of bulky aminophosphanes towards small molecules: Activation of dihydrogen and carbon dioxide by aminophosphane/borane frustrated Lewis pairs
PublicationA series of mono- and bisaminophosphanes with formulas R2NPR’R’’ and (R2N)2PR’ (R = iPr, Cy; R’ = Ph, Cy; R’’ = iPr) were characterized by X-ray analysis, NMR spectroscopy and computational methods. The common structural futures of these species are short and polarized PAN bonds, a pyramidal geometry at the P atom and an almost planar geometry at the N atoms. According to DFT calculations, these...
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Sulfurization of phosphanylphosphinidene ligand: Access to phosphinothioyltrithiophosphonato platinum(II) complexes
PublicationThe reactivity of phosphanylphosphinidene Pt(0) complexes [DppePt(η2-P–PtBu2)] (1) and [(pTol3P)2Pt(η2-P–PtBu2)] (2) toward sulfur was studied. Reactions of 1 and 2 with an excess of sulfur led to the formation of the first transition metal complexes 3 and 4 with phosphinothioyltrithiophosphonato ligands with the formula [tBu2P(=S)–P(=S)S2]2-. In contrast to previous reports on the phosphanylphosphinidene moiety sulfurization,...
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Two complementary approaches for the synthesis and isolation of stable phosphanylphosphaalkenes
PublicationPhospha-Wittig (phosphanylphosphinidene titanium(IV) complex) and phospha-Peterson (lithiated diphosphane) reactions were used to obtain phosphanylphosphaalkenes with the general formula XYC=P-PtBu2 (X = alkyl, aryl group or H; Y = alkyl or aryl group). Therefore, two series of reactions with different ketones and aldehydes were performed. An examination revealed that the two methods are complementary. For smaller carbonyl compounds,...
Year 2020
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Activation of N2O and SO2 by the P–B Bond System. Reversible Binding of SO2 by the P–O–B Geminal Frustrated Lewis Pair
PublicationHerein, we present the first transformation of borylphosphine into borylphosphinite using nitrous oxide. Borylphosphine reacts with N2O via insertion of a single oxygen atom into the P−B bond and formation of a P−O−B bond system. Borylphosphine and borylphosphinite capture SO2 and activate it in an irreversible and reversible manner, respectively.
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Homoleptic mono-, di-, and tetra-iron complexes featuring phosphido ligands: a synthetic, structural, and spectroscopic study
PublicationWe report the first series of homoleptic phosphido iron complexes synthesized by treating either the β-diketiminato complex [(Dippnacnac)FeCl2Li(dme)2] (Dippnacnac = HC[(CMe)N(C6H3-2,6-iPr2)]2) or [FeBr2(thf )2] with an excess of phosphides R2PLi (R = tBu, tBuPh, Cy, iPr). Reaction outcomes depend strongly on the bulkiness of the phosphido ligands. The use of tBu2PLi precursor led to an anionic diiron complex 1 encompassing a planar...
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Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand
PublicationWe present two important trends in the reactivity ofthe titanium complex [MeNacNacTi(Cl){η2-P(SiMe3)-PtBu2}](MeNacNac− = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2Ph)with nucleophilic reagents RLi (R = Ph2P,tBuO, (Me3Si)2N, andtBu2N) depending on the reaction medium. Reaction in nonpolarsolvent (toluene) leads to three main products: via an autoredoxprocess and nucleophilic substitution at the Ti-atom to afford theTi(IV) complex [MeNacNacTi(R){η2-P-PtBu2}]...
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Synthesis of compounds with C-P-P and C=P-P bond systems based on the phospha-Wittig reaction
PublicationA reactivity study of a β-diketiminate titanium(III) phosphanylphosphido complex [MeNacNacTi(Cl){η2-P(SiMe3)-PtBu2}] (1) towards ketones such as benzophenone, 9-fluorenone, acetophenone, cyclopentanone, cyclohexanone and cycloheptanone is reported. The reactions of 1 with aromatic ketones (without α-protons) directly lead to the Ti(III) complex [MeNacNacTi(μ2-Cl)(OSiMe3)] (5) as well as Ti(IV) complexes with the pinacol condensation...
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The Reactivity of Phosphanylphosphinidene Complexes of Transition Metals Toward Terminal Dihaloalkanes
PublicationThe reactivities of phosphanylphosphinidene complexes [(DippN)2W(Cl)(η2-P−PtBu2)]− (1), [(pTol3P)2Pt(η2- P=PtBu2)] (2), and [(dppe)Pt(η2-P=PtBu2)] (3) toward dihaloalkanes and methyl iodide were investigated. The reactions of the anionic tungsten complex (1) with stochiometric Br(CH2)nBr (n = 3, 4, 6) led to the formation of neutral complexes with a tBu2PP(CH2)3Br ligand or neutral dinuclear complexes with unusual tetradentate...
Year 2019
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Diaminophosphinoboranes: effective reagents for phosphinoboration of CO2
PublicationThe monomeric diaminophosphinoboranes readily react with CO2 under mild conditions to cleanly form products of the general formula R2P-C(=O)-O-B(NR2)2 in the absence of a catalyst. The isolated products from the CO2-phosphinoboration were fully characterized by NMR spectroscopy, IR spectroscopy, and X-ray diffraction. The mechanism of CO2 phosphinoboration with diaminophosphinoboranes was elucidated by DFT calculations.
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Diphosphination of CO2 and CS2 mediated by frustrated Lewis pairs - catalytic route to phosphanyl derivatives of formic and dithioformic acid
PublicationThe first example of CO2 diphosphination is described. Reactions of unsymmetrical diphosphanes with CE2 (E = O, S) catalyzed by BPh3 insert a CE2 molecule into the P-P bond with formation of the products of the general formula R2P-E-C(=E)-PR2. The obtained CO2 adducts arise from synergistic interaction of diphosphane and borane with CO2 molecule.
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Molecular Structures of the Phospha-Wittig Reaction Intermediate: Initial Step in the Synthesis of Compounds with a C═P–P Bond as Products in the Phospha-Wittig Reaction
PublicationThe phospha-Wittig reactivity ofβ-diketiminate titanium(III) complexes with phosphanylphosphido ligands was investigated. The reactions of [MeNacNacTi(Cl){η2-P(SiMe3)-PtBu2}] and [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] with acetone conducted in toluene solution under mild conditions led to the phospha-Wittig intermediates [{(ArN=C(Me)CHC(Me)=NAr)(C(Me)2O}Ti(Cl){PtBu2-P(SiMe3)C(Me)2O}] (1) and [{(ArN=C(Me)CHC(Me)=NAr) (C-(Me)2O}Ti(Cl){P(Ph)tBu-P(SiMe3)C(Me)2O}]...
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Reactivity study of a β-diketiminate titanium(III) complex with a phosphanylphosphido ligand towards chlorophosphanes. A new method of synthesis of β-diketiminate titanium(IV) complexes with versatile phosphanylphosphinidenes
PublicationThe reactivity of ab-diketiminate titanium(III) complex with a phosphanylphosphido ligand, [MeNacNacTi(Cl){g2-P(SiMe3)-PtBu2}] (1)(MeNacNac= [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2Ph), was investigatedtowards selected chlorophosphanes, such astBu2PCl,iPr2PCl, Cy2PCl, (Cy)tBuPCl, (Me)tBuPCl, (Ph)tBuPCl, Ph2PCl, (iPr2N)tBuPCl and (Et2N)2PCl. The reactions withtBu2PCl and Ph2PCl lead mainly to theearlier described complex [MeNacNacTi(Cl){g2-P-PtBu2}]...
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Structural and spectroscopic analysis of a new family of monomeric diphosphinoboranes
PublicationWe present a series of amino- and aryl(diphosphino)boranes R2PB(R’’)PR’2, where R2P, R’2P = tBu2P, tBuPhP, Ph2P, Cy2P, and R’’ = iPr2N, Ph, which were obtained via the metathesis reaction of iPr2NBBr2 or PhBBr2 with selected lithium phosphides. The structures of isolated diphosphinoboranes were characterized in the solid state and in solution by means of X-ray diffraction and NMR spectroscopy, respectively. The utility of these...
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Syntheses and Structures of Transition Metal Complexes with Phosphanylphosphinidene Chalcogenide Ligands
PublicationThe reactivity of the phosphanylphosphinidene complex [(DippN)2W(Cl)(η2-P-PtBu2)]− (1) toward chalcogens (Ch = Se, S) was studied. Reactions of stoichiometric amounts of 1 with chalcogens in DME yielded monomeric tungsten complexes with phosphanylphosphinidene chalcogenide ligands of the formula tBu2P−P−Ch (Ch = Se (in 2) and S (in 5)), which can be regarded as products of the addition of a chalcogen atom to a P=W bond in starting...
Year 2018
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Reactions of (Ph)tBuP-P(SiMe3)Li·3THF with [(PNP)TiCl2] and [MeNacNacTiCl2·THF]. Synthesis of first PNP titanium(IV) complex with phosphanylphosphinidene ligand [(PNP)Ti(Cl){η2-P-P(Ph)tBu}]
PublicationLithium derivative of diphosphane (Ph)tBuP-P(SiMe3)Li (1) was isolated for the first time and investigated in reactions with β-diketiminate (MeNacnac− = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2C6H3) and PNP-pincer (PNP = N[2-PiPr2-4-methylphenyl]2) Ti(III) complexes. The β-diketiminate titanium(III) complex containing phosphanylphosphido ligand [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2) was prepared in reaction of [MeNacNacTiCl2·THF]...
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Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl and amino substituents
PublicationWe present the comprehensive study of diphosphanes with diversified substituents regarding their syntheses, structures, and properties. To this end, we have synthesized a series of novel unsymmetrical alkyl, aryl and amino-substituted diphosphanes of the general formula R1R2P-PR3R4 (where R1, R2, R3, R4 = tBu, Ph, Et2N or iPr2N) via salt metathesis reactionof halophosphanes with metal phosphides in high yield. We vastly expanded...
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