Phosphinophosphoranes: Mixed-Valent Phosphorus Compounds with Ambiphilic Properties.

Herein, 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 lone-pair electrons on the P-phosphanyl atom of phosphinophosphoranes during the reaction of the title compounds with H3B·SMe2, where phosphinophosphorane-borane adducts were formed quantitatively, was confirmed. Furthermore, the Lewis basic and Lewis acidic properties of the phosphinophosphoranes in reactions with phenyl isothiocyanate were tested. Depending on the structure of the starting phosphinophosphorane, phosphinophosphorylation of PhNCS or formation of a five-membered zwitterionic adduct was observed. The structures of the isolated compounds were unambiguously determined by heteronuclear nuclear magnetic resonance spectroscopy and single-crystal X-ray diffraction. Moreover, by applying density functional theory calculations, we compared the Lewis basicity and nucleophilicity of diversified trivalent P-centers.

Phosphinoborinium cation: a synthon for cationic B-P bond systems.

Herein, 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 B2P2 core. Activation of the C-H and C-P bonds in the dication led to the formation of the borinium-phosphaborene adduct. Reactivity studies revealed that the title cation exhibits ambiphilic properties and intramolecular frustrated Lewis pair features.

Exploring the Reactivity of Unsymmetrical Diphosphanes toward Heterocumulenes: Access to Phosphanyl and Phosphoryl Derivatives of Amides, Imines, and Iminoamides.

We 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 X-ray diffraction. We showed that unsymmetrical diphosphanes could be used as building blocks to synthesize phosphorus analogues of important classes of organic molecules. The described transformations provided a new methodology for the synthesis of organophosphorus compounds bearing phosphanyl, phosphoryl, or thiophosphoryl functional groups. Moreover, theoretical studies on diphosphanation reactions explained the influence of the steric and electronic properties of the parent diphosphanes on the structures of the diphosphanation products.

Activation of the C[double bond, length as m-dash]P bond in phosphanylphosphaalkenes (C[double bond, length as m-dash]P-P bond system) in the reaction with nucleophilic reagents: MeLi, nBuLi and tBuLi.

Three 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-(PtBu2)]- (1a'') and [P(nBu)2-CH(biph)-CH(biph)-P-(PtBu2)]- (1b''), respectively, are formed depending on the nucleophilic reagent (biph = biphenyl). In the case of tBuLi, the P-P bond remains intact; on the phosphorus atom, only one -tBu group is substituted, and as a result, [(biph)(H)C-P(tBu)-PtBu2]- (1c) is generated as a stable carbanion. We additionally investigated the effect of substitution in the phenyl ring in the course of these reactions by involving two other phosphanylphosphaalkenes (3 and 4). All initial reactions were conducted in tetrahydrofuran (THF) solution at ambient temperature.

Monomeric Triphosphinoboranes: Intramolecular Lewis Acid-Base Interactions between Boron and Phosphorus Atoms.

Herein, we present the synthesis of the first fully characterized monomeric triphosphinoboranes. The simple reaction of boron tribromide with 3 equiv 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 1 equiv of less bulky phosphide R2PLi (R2P = Cy2P, iPr2P, tBuPhP, or Ph2P). By utilizing this method, we obtained a series of triphosphinoboranes with the general formula (tBu2P)2BPR2. On the basis of structural and theoretical studies, two main types of triphosphinoborane structures can be distinguished. In the first type, all three electron lone pairs interact with the formally empty p orbital of the central boron atom, resulting in delocalized π bonding, whereas in the second type, one localized P═B bond and two P-B bonds are observed. The Lewis acidic-basic properties of triphosphinoboranes during the reaction of (tBu2P)2BPiPr2 with H3B·SMe2 were analyzed. The P-B bond-containing compound mentioned above not only formed an adduct with BH3 but also activated the B-H bond of the borane molecule, resulting in the incorporation of the BH2 unit into two phosphorus atoms and migration of a hydride to the boron atom of the parent triphosphinoborane. The structures of the triphosphinoboranes were confirmed by single-crystal X-ray analysis, multinuclear nuclear magnetic resonance spectroscopy, and elemental analysis.

Diphosphinoboranes as Intramolecular Frustrated Lewis Pairs: P-B-P Bond Systems for the Activation of Dihydrogen, Carbon Dioxide, and Phenyl Isocyanate.

Herein, 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, (t-Bu2P)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 a catalyst with the formation of the dimer (t-Bu2PB(Ph)H)2 and t-Bu2PH. Conversely, diphosphinoborane 2 did not react with H2 under the same conditions. The reaction of 1' with CO2 led to the formation of a compound with an unusual structure, where two phosphinoformate units were coordinated to the PhBOBPh moiety. In addition, 2 reacted with CO2 to insert two CO2 molecules into the P-B bonds of the parent diphosphinoborane. Both diphosphinoboranes activated PhNCO, yielding products resulting from the addition of two and/or three PhNCO molecules and the formation of new P-C, B-O, B-N, and C-N bonds. The products of the activation of small molecules by diphosphinoboranes were characterized with nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, single-crystal X-ray diffraction, and elemental analysis. Additionally, the reaction mechanisms of the activation of small molecules by diphosphinoboranes were elucidated by theoretical methods.

Experimental and theoretical investigation of the reactivity of [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2}] towards selected ketones.

In this work, we report a new type of reactivity of [(BDI*)Ti(Cl){η2-P(SiMe3)-PiPr2}] (1) towards ketones (BDI* = 2,6-diisopropylphenyl-ß-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}] (2b), [(BDI*)Ti(Cl){η2-P(SiMe3)-P(iPr)2-{C(CH2)4}O}] (3a), and [(BDI*)Ti(Cl){η2-P(SiMe3)-P(iPr)2-{C(CH2)5}O}] (4a). Starting complex 1 reacts with cyclohexanone, yielding a monocrystalline complex [{(ArN[double bond, length as m-dash]C(Me)CHC(Me)[double bond, length as m-dash]NAr)C(CH2)5O}Ti(Cl){PiPr2-P(SiMe3)C(CH2)5O}] (4d) with the insertion of two ketone molecules. Interestingly, we found that monoinserted complexes 2a and 3a may be oxidized via a reaction with AgCl, leading to elimination of the -SiMe3 group and oxidation of the titanium atom. This reaction led us to isolate the Ti(iv) complex [(BDI*)Ti(Cl){η2-P-P(iPr)2-{C(CH2)5}O}] (5) in crystalline form. To identify the kinds of products that may be formed and determine which products are the most energetically favoured ones, we conducted a thermodynamic DFT study of 1 towards acetone, cyclopentanone and cyclohexanone. Structures 2a, 2b, 3a, 3e, 4a, 4d, and 5 were characterized by X-ray crystallography, and complex 5 was also identified by NMR spectroscopy.

Synthesis of compounds with C-P-P and C[double bond, length as m-dash]P-P bond systems based on the phospha-Wittig reaction.

A reactivity study of a ß-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) and Ti(iv) complexes with the pinacol condensation product [MeNacNacTi(OSiMe3)(η2-pinacolate)] (3), and phosphanylphosphaalkenes Ph2C[double bond, length as m-dash]P-PtBu2 (2) and (fluorenyl)C[double bond, length as m-dash]P-PtBu2 (6), respectively. The reaction with acetophenone leads to the titanium(iii) complex with the aldol condensation product as ligand [MeNacNacTi(Cl){OC{Me(Ph)}CH2(C[double bond, length as m-dash]O)Ph}] (8) and in parallel to phosphanylphosphaalkene (Ph)MeC[double bond, length as m-dash]P-PtBu2 (9) and 5. The reactions of 1 with cyclic ketones (cyclopentanone and cyclohexanone) lead to Ti(iii) complexes [{(ArN[double bond, length as m-dash]C(Me)CHC(Me)[double bond, length as m-dash]NAr)((CH2)4CO)}Ti(Cl){PtBu2-P(SiMe3)((CH2)4CO)}] (10) and [{(ArN[double bond, length as m-dash]C(Me)CHC(Me)[double bond, length as m-dash]NAr)((CH2)5CO)}Ti(Cl){PtBu2-P(SiMe3)((CH2)5CO)}] (11), which are formed via the successive insertion of two molecules of ketone to one molecule of 1. The stability investigation of complexes 10 and 11 in a polar solvent (THF) revealed that under these conditions, the complexes decompose, resulting in titanium(iii) complexes with aldol condensation products and the expected phosphanylphosphaalkenes (CH2)4C[double bond, length as m-dash]P-PtBu2 (10a) and (CH2)5C[double bond, length as m-dash]P-PtBu2 (11a). In the reaction of 1 with cycloheptanone, only the Ti(iii) complex with the aldol condensation product [MeNacNacTi(Cl){OC(CH2)6}CH(C[double bond, length as m-dash]O)(CH2)5] (12) was isolated. The structures 3, 5, 8, 10, 11, 11b and 12 were characterized by X-ray spectroscopy, while all the phosphanylphosphaalkenes were characterized by NMR spectroscopy.

Homoleptic mono-, di-, and tetra-iron complexes featuring phosphido ligands: a synthetic, structural, and spectroscopic study.

We report the first series of homoleptic phosphido iron complexes synthesized by treating either the ß-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 Fe2P2 core with two bridging and two terminal phosphido ligands. An analogous reaction employing less sterically demanding phosphides, tBuPhPLi and Cy2PLi yielded diiron anionic complexes 2 and 3, respectively, featuring a short Fe-Fe interaction supported by three bridging phosphido groups and one additional terminal R2P- ligand at each iron center. Further tuning of the P-substrates bulkiness gave a neutral phosphido complex 4 possessing a tetrahedral Fe4 cluster core held together by six bridging iPr2P moieties. Moreover, we also describe the first homoleptic phosphanylphosphido iron complex 5, which features an iron center with low coordination provided by three tBu2P-P(SiMe3)- ligands. The structures of compounds 1-5 were determined by single-crystal X-ray diffraction and 1-3 by 1H NMR spectroscopy. Moreover, the electronic structures of 1-3 were interrogated using zero-field Mössbauer spectroscopy and DFT methods.

Activation of N2O and SO2 by the P-B Bond System. Reversible Binding of SO2 by the P-O-B Geminal Frustrated Lewis Pair.

Herein, 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.

The Reactivity of Phosphanylphosphinidene Complexes of Transition Metals Toward Terminal Dihaloalkanes.

The 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 tBu2PP(CH2)nPPtBu2 ligands (n = 4, 6). The methylation of platinum complexes 2 and 3 with MeI yielded neutral or cationic complexes bearing side-on coordinated tBu2P-P-Me moieties. The reaction of 2 with I(CH2)2I gave a platinum complex with a tBu2P-P-I ligand. When the same dihaloalkane was reacted with 3, the P-P bond in the phosphanylphosphinidene ligand was cleaved to yield tBu2PI, phosphorus polymers, [(dppe)PtI2] and C2H4. Furthermore, the reaction of 3 with Br(CH2)2Br yielded dinuclear complex bearing a tetraphosphorus tBu2PPPPtBu2 ligand in the coordination sphere of the platinum. The molecular structures of the isolated products were established in the solid state and in solution by single-crystal X-ray diffraction and NMR spectroscopy. DFT studies indicated that the polyphosphorus ligands in the obtained complexes possess structures similar to free phosphenium cations tBu2P+═P-R (R = Me, I) or (tBu2P+═P)2.

Structural and spectroscopic analysis of a new family of monomeric diphosphinoboranes.

We 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 P-B-P species as ligands for transition metal complexes was tested in the reaction with [(COD)PtMe2]. Moreover, we carried out DFT calculations to elucidate bonding interactions and philicity of the reactive centers as well as to analyze conformations of the studied species. Electronic and steric properties of substituents on P and B atoms were found to have a strong influence on the structures of the obtained compounds. Three main types of diphosphinoboranes were distinguished, based on the strength of P-B π-interaction within the molecule: (i) application of strong electron-donating substituents on P-atoms and electron-accepting phenyl groups on B atoms led to the structure with one double P[double bond, length as m-dash]B and one single P-B bond and diverse planar and pyramidal geometry of phosphanyl groups; (ii) reduction of the donor ability of phosphanyl groups gave diphosphanylboranes with delocalized P-B-P π-interactions; (iii) introduction of amino groups with strong donor abilities on B atoms canceled P-B π-interactions and allowed compounds with two very long P-B bonds and two pyramidal phosphanyl groups to be obtained.

Syntheses and Structures of Transition Metal Complexes with Phosphanylphosphinidene Chalcogenide Ligands.

The reactivity of the phosphanylphosphinidene complex [(DippN)2W(Cl)(η2-P-P tBu2)]- (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 complex 1. The dissolution of selenophosphinidene complex 2 in nondonor solvents led to the formation of a dinuclear complex of tungsten (3) bearing a tBu2P(Se)-P ligand together with [ tBuSe2Li(dme)2]2 and polyphosphorus species. Under the same reaction conditions, thiophosphinidene complex 5 dimerized via the formation of transient complex 7, possessing a thiotetraphosphane-diido moiety tBu2P(S)-P-P-P tBu2. The elimination of the tBu2PS group from 7 yielded stable dinuclear tungsten complex 8 with an unusual phosphinidene tBu2P-P-P ligand. The reaction of 1 with excess chalcogen led to the cleavage of the P-P bond in the tBu2P-P ligand and the formation of [(DippN)2W(PCh4)]22- and [ tBuCh2Li(dme)2]2. The isolated compounds were characterized by NMR spectroscopy and X-ray crystallography. Furthermore, the calculated geometries of the free selenophosphinidenes, tBu2P-P-Se and tBu2P(Se)-P, were compared with their geometries when serving as ligands in complexes 2 and 3.

Diphosphination of CO2 and CS2 mediated by frustrated Lewis pairs - catalytic route to phosphanyl derivatives of formic and dithioformic acid.

The 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([double bond, length as m-dash]E)-PR2. The obtained CO2 adducts arise from synergistic interaction of diphosphane and borane with CO2 molecule.

Diaminophosphinoboranes: effective reagents for phosphinoboration of CO2.

The monomeric diaminophosphinoboranes readily react with CO2 under mild conditions to cleanly form products of the general formula 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.

Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl, and amino substituents.

We 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 a salt metathesis reaction of halophosphanes with metal phosphides in high yield. We vastly expanded this group of compounds by obtaining the first mono- and tri-amino-substituted systems. The structures of the isolated compounds were characterized by NMR spectroscopy and X-ray diffraction. The isolated unsymmetrical diphosphanes have no tendency to rearrange to the corresponding symmetrical species. Additionally, we proposed the general classification of diphosphanes based on the number of different groups attached to phosphorus atoms and their distribution within a molecule. To investigate the impact of substituents on the properties of P-centers and a molecule as a whole, we conducted a DFT study on the electronic and steric properties of the obtained systems. The experimental and theoretical results can be very useful for designing P-P systems with desired properties.

Reactions of (Ph)tBuP-P(SiMe3)Li·3THF with [(PNP)TiCl2] and [MeNacNacTiCl2·THF]: synthesis of first PNP titanium(iv) complex with the phosphanylphosphinidene ligand [(PNP)Ti(Cl){η2-P-P(Ph)tBu}].

Herein, the lithium derivative of diphosphane, (Ph)tBuP-P(SiMe3)Li (1), is isolated for the first time and investigated in reactions with ß-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 ß-diketiminate titanium(iii) complex containing the phosphanylphosphido ligand [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2) is prepared via the reaction of [MeNacNacTiCl2·THF] with (Ph)tBuP-P(SiMe3)Li in toluene solution with good yield and purity. The corresponding titanium(iv) complex involving the phosphanylphosphinidene ligand [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) is synthesized via the oxidation of complex (2) with [iBu3PAgCl]4. Interestingly, an analogous PNP titanium(iv) complex, [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] (4), is obtained in the reaction of [(PNP)TiCl2] with (Ph)tBuP-P(SiMe3)Li in toluene solution and a 1 : 1 molar ratio instead of the expected titanium(iii) complex with the phosphanylphosphido ligand. The solid-state structures of (Ph)tBuP-P(SiMe3)Li·3THF (1), [MeNacNacTi(Cl){η2-P(SiMe3)-P(Ph)tBu}] (2), [MeNacNacTi(Cl){η2-P-P(Ph)tBu}] (3) and [(PNP)Ti(Cl){η2-P-P(Ph)tBu}] (4) are determined by single-crystal X-ray diffraction, which reveals that in all obtained complexes, both the phosphanylphosphinidene (Ph)tBuP-P and phosphanylphosphido (Ph)tBuP-P(SiMe3) ligands are bidentate-coordinated to the metal center.