Phosphinidene

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General structure of a phosphinidene Phosphinidene.png
General structure of a phosphinidene

Phosphinidenes (IUPAC: phosphanylidenes, formerly phosphinediyls) are low-valent phosphorus compounds analogous to carbenes and nitrenes, having the general structure RP. [1] [2] The parent phosphinidine has the formula PH. More common are the organic analogues where R = alkyl or aryl. In these compounds phosphorus has only 6 electrons in its valence level. [2] Most phosphinidenes are highly reactive and short-lived, thereby complicating empirical studies on their chemical properties. [3] [4]

Contents

A variety of strategies have been employed to stabilize phosphinidenes (e.g. π-donation.steric protection, transition metal complexation), [2] [3] Furthermore reagents and systems have been developed that can generate and transfer phosphinidenes as intermediates in the synthesis of various organophosphorus compounds. [5] [6] [7] [8]

Electronic structure

Singlet and Triplet Phosphinidenes Phosphinidene singlet triplet.png
Singlet and Triplet Phosphinidenes

Like carbenes, phosphinidenes can exist in either a singlet state or triplet state, with the triplet state typically being more stable. [2] [4] The stability of these states and their relative energy difference (the singlet-triplet energy gap) depends on the substituents. The ground state in the parent phosphinidene (PH) is a triplet that is 22 kcal/mol more stable than the lowest singlet state. [2] [9] This singlet-triplet energy gap is considerably larger than that of the simplest carbene methylene (9 kcal/mol). [10]

Ab initio calculations from Nguyen et al. found that alkyl- and silyl-substituted phosphinidenes have triplet ground states, possibly in-part due to a negative hyperconjugation. [4] Substituents containing lone pairs (e.g. -NX2, -OX, -PX2 ,-SX) stabilize the singlet state, presumably by π-donation into an empty phosphorus 3p orbital; in most of these cases, the energies of the lowest singlet and triplet states were close to degenerate. [4] A singlet ground state could be induced in amino- and phosphino-phosphinidenes by introducing bulky β-substituents, which are thought to destabilize the triplet state by distorting the pyramidal geometry through increased nuclear repulsion. [4]

Case studies

Dibenzo-7-phosphanorbornadiene derivatives

One way to generate phosphinidines employs the decyclization of phosphaanthracene complexes. [11]

Treatment of a bulky phosphine chloride (RPCl2) with magnesium anthracene affords a dibenzo-7-phosphanorbornadiene compound (RPA). [11] Under thermal conditions, the RPA compound (R = NiPr2) decomposes to yield anthracene; kinetic experiments found this decomposition to be first-order. [11] It was hypothesized that the amino-phosphinidene iPr2NP is formed as a transient intermediate species, and this was corroborated by an experiment where 1,3-cyclohexadiene was used as a trapping agent, forming anti-iPr2NP(C6H8). [11]

Synthesis of RPA (R = NiPr2) and an example phosphinidene transfer reaction with 1,3-cyclohexadiene RPA reaction.png
Synthesis of RPA (R = NiPr2) and an example phosphinidene transfer reaction with 1,3-cyclohexadiene

Molecular beam mass spectrometry has enabled the detection of the evolution of amino-phosphinidene fragments from a number of alkylamide derivatives (e.g. Me2NP+ and Me2NPH+ from Me2NPA) in the gas-phase at elevated temperatures. [5]

Phosphino-phosphinidene

The first singlet phosphino-phosphinidene has been prepared using extremely bulky substituents. [3] The authors prepared a chlorodiazaphospholidine with bulky (2,6-bis[(4-tert-butylphenyl)methyl]-4-methylphenyl) groups, and then synthesized the corresponding phosphaketene. Subsequent photolytic decarbonylation of the phosphaketene produced the phosphino-phosphinidene product as a yellow-orange solid that is stable at room temperature but decomposes immediately in the presence of air and moisture. [3] 31P NMR spectroscopy shows assigned product peaks at 80.2 and -200.4 ppm, with a J-coupling constant of JPP = 883.7 Hz. The very high P-P coupling constant is indicative of P-P multiple bond character. [3] The air/water sensitivity and high solubility of this compound prevented characterization by X-ray crystallography. [3]

Synthesis of a stable singlet phospino-phosphinidene with bulky 2,6-bis[4-tert-butylphenyl)methyl]-4-methylphenyl substituents as reported by Bertrand and coworkers. Stable phosphinidene1.png
Synthesis of a stable singlet phospino-phosphinidene with bulky 2,6-bis[4-tert-butylphenyl)methyl]-4-methylphenyl substituents as reported by Bertrand and coworkers.

Density functional theory and Natural bond orbital (NBO) calculations were used to gain insight into the structure and bonding of these phosphino-phosphinidenes. DFT calculations at the M06-2X/Def2-SVP level of theory on the phospino-phosphinidene with bulky 2,6-bis[4-tert-butylphenyl)methyl]-4-methylphenyl groups suggest that the tri-coordinated phosphorus atom exists in a planar environment. [3] Calculations at the M06-2X/def2-TZVPP//M06-2X/def2-SVP level of theory were applied to a simplified model compound with diisopropylphenyl (Dipp) groups so as to reduce the computational cost for detailed NBO analysis. [3] Inspection of the outputted wavefunctions shows that the HOMO and HOMO-1 are P-P π-bonding orbitals and the LUMO is a P-P π*-antibonding orbital. [3] Further evidence of multiple bond character between the phosphorus atoms was provided by natural resonance theory and a large Wiberg bond index (P1-P2: 2.34). [3] Natural population analysis assigned a negative partial charge to the terminal phosphorus atom (-0.34 q) and a positive charge to the tri-coordinated phosphorus atom (1.16 q). [3]

Frontier molecular orbitals of a model phosphino-phosphinidene with "Dipp" groups. Calculations were performed at the M06-2X/def2-TZVPP//M06-2X/def2-SVP level of theory. Reproduced from Bertrand and coworkers with NBO 6.0 in ORCA. 4.2.0 and visualized in IBOview. Bertrand phosphinidene HOMO-LUMO.png
Frontier molecular orbitals of a model phosphino-phosphinidene with "Dipp" groups. Calculations were performed at the M06-2X/def2-TZVPP//M06-2X/def2-SVP level of theory. Reproduced from Bertrand and coworkers with NBO 6.0 in ORCA. 4.2.0 and visualized in IBOview.

Despite the negative charge on the terminal phosphorus atom, subsequent studies have shown that this particular phosphinidene is electrophilic at the phosphinidene center. This phosphino-phosphinidene reacts with a number of nucleophiles (CO, isocyanides, carbenes, phosphines, etc.) to form phosphinidene-nucleophile adducts [3] [12] Upon nucleophilic addition, the tri-coordinated phosphorus atom becomes non-planar, and it is postulated that the driving force of the reaction is provided by the instability of the phosphinidene's planar geometry. [12]

Reactivity of phosphino-phosphinidene with various nucleophiles Reactivity of phosphinidene.png
Reactivity of phosphino-phosphinidene with various nucleophiles

Phospha-Wittig fragmentation

Dominant resonance structures of the phospha-Wittig reagent from Fritz et al. Phosphawittig.png
Dominant resonance structures of the phospha-Wittig reagent from Fritz et al.

In 1989, Fritz et al. synthesized the phospha-Wittig species shown to the right. [13] Phospha-Wittig compounds can be viewed as a phosphinidene stabilized by a phosphine. These compounds have been given the label of "phospha-Wittig" as they have two dominant resonance structures (a neutral form and a zwitterionic form) that are analogous to those of the phosphonium ylides that are used in the Wittig reaction.

Fritz et al. found that this particular phospha-Wittig reagent thermally decomposes at 20 °C to give tBu2PBr, LiBr, and cyclophosphanes. [13] The authors proposed that the singlet phosphino-phosphinidene tBu2PP was formed as an intermediate in this reaction. Further evidence for this was provided by trapping experiments, where the thermal decomposition of the phospha-Wittig reagent in the presence of 3,4,-dimethyl-1,3-butadiene and cyclohexene gave rise to the products shown in the figure below. [13]

Reactivity of the phopha-Wittig reagent as described in Fritz et al. Phosphawittig reactions.png
Reactivity of the phopha-Wittig reagent as described in Fritz et al.

Metal complexes

Terminal phosphinidine complexes

Terminal transition-metal-complexed phosphinidenes LnM=P-R are phosphorus analogs of transition metal carbene complexes. The first "metal-phosphinidine" was reported by Marinetti et al. They generated the transient species [(OC)5M=P-Ph] by fragmentation of 7-phosphanorbornadiene molybdenum and tungsten complexes inside a mass spectrometer. [14] [15] Soon after, they discovered that these 7-phosphanorbornadiene complexes could be used to transfer the phosphinidene complex [(OC)5M=P-R] to various unsaturated substrates. [15] [16]

Synthesis and reactivity of several 7-phosphanorbornadiene complexes 7-phosphanorbornadiene synthesis and reaction.png
Synthesis and reactivity of several 7-phosphanorbornadiene complexes

Donor-stabilized terminal phosphinidene complexes are also known, [17] which could release free phosphinidene complexes LnM=P-R at mild conditions by P-donor dissociation reactions. [18] [19] The phosphinidene complexes decomposed to white phosphorus if no unsaturated substrates were provided. [18]

Synthesis and reactivity of donor-to-phosphinidene complex adducts. Synthesis+reactivity Do-to-phosphinidene complex adducts.png
Synthesis and reactivity of donor-to-phosphinidene complex adducts.

Terminal phosphinidene complexes of the type Cp2M=P-R (M = Mo, W) can be obtained by combining aryl-dichlorophosphines RPCl2 with [Cp2MHLi]4. [20]

Lappert and coworkers' synthesis of first stable terminal phosphinidene complex Lappert metallocene phosphinidene.png
Lappert and coworkers' synthesis of first stable terminal phosphinidene complex

Phosphinidine-based clusters

Metal clusters containing RP substituents are numerous. They typically arise by the reaction of metal carbonyls with primary phosphines (compounds with the formula RPH2). A partucularly well-studied case is Fe3(PC6H5)2(CO)9, which forms from iron pentacarbonyl and phenylphosphine according to the following idealized equation: [21]

3 Fe(CO)5 + 2 C6H5PH2 → Fe3(PC6H5)2(CO)9 + 2 H2 + 6 CO

A related example is the tert-butylphosphinidene complex (t-BuP)Fe3(CO)10. [22]

See also

Related Research Articles

An ylide or ylid is a neutral dipolar molecule containing a formally negatively charged atom (usually a carbanion) directly attached to a heteroatom with a formal positive charge (usually nitrogen, phosphorus or sulfur), and in which both atoms have full octets of electrons. The result can be viewed as a structure in which two adjacent atoms are connected by both a covalent and an ionic bond; normally written X+–Y−. Ylides are thus 1,2-dipolar compounds, and a subclass of zwitterions. They appear in organic chemistry as reagents or reactive intermediates.

In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is R−:C−R' or R=C: where the R represents substituents or hydrogen atoms.

A transition metal carbene complex is an organometallic compound featuring a divalent carbon ligand, itself also called a carbene. Carbene complexes have been synthesized from most transition metals and f-block metals, using many different synthetic routes such as nucleophilic addition and alpha-hydrogen abstraction. The term carbene ligand is a formalism since many are not directly derived from carbenes and most are much less reactive than lone carbenes. Described often as =CR2, carbene ligands are intermediate between alkyls (−CR3) and carbynes (≡CR). Many different carbene-based reagents such as Tebbe's reagent are used in synthesis. They also feature in catalytic reactions, especially alkene metathesis, and are of value in both industrial heterogeneous and in homogeneous catalysis for laboratory- and industrial-scale preparation of fine chemicals.

Diphosphene is a type of organophosphorus compound that has a phosphorus–phosphorus double bond, denoted by R-P=P-R'. These compounds are not common, but their properties have theoretical importance.

<span class="mw-page-title-main">Phosphaalkyne</span>

In chemistry, a phosphaalkyne is an organophosphorus compound containing a triple bond between phosphorus and carbon with the general formula R-C≡P. Phosphaalkynes are the heavier congeners of nitriles, though, due to the similar electronegativities of phosphorus and carbon, possess reactivity patterns reminiscent of alkynes. Due to their high reactivity, phosphaalkynes are not found naturally on earth, but the simplest phosphaalkyne, phosphaethyne (H-C≡P) has been observed in the interstellar medium.

<span class="mw-page-title-main">Persistent carbene</span> Type of carbene demonstrating particular stability

A persistent carbene is an organic molecule whose natural resonance structure has a carbon atom with incomplete octet, but does not exhibit the tremendous instability typically associated with such moieties. The best-known examples and by far largest subgroup are the N-heterocyclic carbenes (NHC), in which nitrogen atoms flank the formal carbene.

Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to humans, including sarin and VX nerve agents.

Carbene analogs in chemistry are carbenes with the carbon atom replaced by another chemical element. Just as regular carbenes they appear in chemical reactions as reactive intermediates and with special precautions they can be stabilized and isolated as chemical compounds. Carbenes have some practical utility in organic synthesis but carbene analogs are mostly laboratory curiosities only investigated in academia. Carbene analogs are known for elements of group 13, group 14, group 15 and group 16.

<span class="mw-page-title-main">Germylene</span> Class of germanium (II) compounds

Germylenes are a class of germanium(II) compounds with the general formula :GeR2. They are heavier carbene analogs. However, unlike carbenes, whose ground state can be either singlet or triplet depending on the substituents, germylenes have exclusively a singlet ground state. Unprotected carbene analogs, including germylenes, has a dimerization nature. Free germylenes can be isolated under the stabilization of steric hindrance or electron donation. The synthesis of first stable free dialkyl germylene was reported by Jutzi, et al in 1991.

Methylene is an organic compound with the chemical formula CH
2. It is a colourless gas that fluoresces in the mid-infrared range, and only persists in dilution, or as an adduct.

<span class="mw-page-title-main">Cyclic alkyl amino carbenes</span>

Cyclic(alkyl)(amino) carbenes (CAACs) are a class of stable singlet carbene ligands that feature one amino and one sp3 alkyl group adjacent to the carbene carbon atom. CAACs are a subset of N-heterocyclic carbenes (NHCs) in which the replacement of an amino group on the "classical" diaminocarbene with a saturated carbon atom results in a carbene ligand that is both a better σ-donor and π-acceptor than classical NHCs. The lone pair on the nitrogen atoms in classical NHCs allows for π-donation from both nitrogen atoms, while substitution of one nitrogen with a carbon atom results in weaker π-donation from only one nitrogen substituent, thus making CAACs stronger π-acceptors and more electrophilic than classical NHCs. Like NHCs, CAACs have tunable steric and electronic properties that make them versatile ligands in both transition metal and main group. CAACs have been heavily studied. CAACs form stable adducts with otherwise reactive or unstable molecules. In materials science, CAACs stabilize species that have promising photophysical properties for organic light emitting diodes (OLEDs) and have been shown to stabilize single molecule magnets (SMMs).

A phosphetane is a 4-membered organophosphorus heterocycle. The parent phosphetane molecule, which has the formula C3H7P, is one atom larger than phosphiranes, one smaller than phospholes, and is the heavy-atom analogue of azetidines. The first known phosphetane synthesis was reported in 1957 by Kosolapoff and Struck, but the method was both inefficient and hard to reproduce, with yields rarely exceeding 1%. A far more efficient method was reported in 1962 by McBride, whose method allowed for the first studies into the physical and chemical properties of phosphetanes. Phosphetanes are a well understood class of molecules that have found broad applications as chemical building blocks, reagents for organic/inorganic synthesis, and ligands in coordination chemistry.

<span class="mw-page-title-main">Phosphenium</span> Divalent cations of phosphorus

Phosphenium ions, not to be confused with phosphonium or phosphirenium, are divalent cations of phosphorus of the form [PR2]+. Phosphenium ions have long been proposed as reaction intermediates.

A transition metal phosphido complex is a coordination complex containing a phosphido ligand (R2P, where R = H, organic substituent). With two lone pairs on phosphorus, the phosphido anion (R2P−) is comparable to an amido anion (R2N−), except that the M-P distances are longer and the phosphorus atom is more sterically accessible. For these reasons, phosphido is often a bridging ligand. The -PH2 ion or ligand is also called phosphanide or phosphido ligand.

1-Phosphaallenes is are allenes in which the first carbon atom is replaced by phosphorus, resulting in the structure: -P=C=C<.

<i>m</i>-Terphenyl Organic ligand

m-Terphenyls (also known as meta-terphenyls, meta-diphenylbenzenes, or meta-triphenyls) are organic molecules composed of two phenyl groups bonded to a benzene ring in the one and three positions. The simplest formula is C18H14, but many different substituents can be added to create a diverse class of molecules. Due to the extensive pi-conjugated system, the molecule it has a range of optical properties and because of its size, it is used to control the sterics in reactions with metals and main group elements. This is because of the disubstituted phenyl rings, which create a pocket for molecules and elements to bond without being connected to anything else. It is a popular choice in ligand, and the most chosen amongst the terphenyls because of its benefits in regards to sterics. Although many commercial methods exist to create m-terphenyl compounds, they can also be found naturally in plants such as mulberry trees.

<span class="mw-page-title-main">Stable phosphorus radicals</span>

Stable and persistent phosphorus radicals are phosphorus-centred radicals that are isolable and can exist for at least short periods of time. Radicals consisting of main group elements are often very reactive and undergo uncontrollable reactions, notably dimerization and polymerization. The common strategies for stabilising these phosphorus radicals usually include the delocalisation of the unpaired electron over a pi system or nearby electronegative atoms, and kinetic stabilisation with bulky ligands. Stable and persistent phosphorus radicals can be classified into three categories: neutral, cationic, and anionic radicals. Each of these classes involve various sub-classes, with neutral phosphorus radicals being the most extensively studied. Phosphorus exists as one isotope 31P (I = 1/2) with large hyperfine couplings relative to other spin active nuclei, making phosphorus radicals particularly attractive for spin-labelling experiments.

A ketenyl anion contains a C=C=O allene-like functional group, similar to ketene, with a negative charge on either terminal carbon or oxygen atom, forming resonance structures by moving a lone pair of electrons on C-C-O bond. Ketenes have been sources for many organic compounds with its reactivity despite a challenge to isolate them as crystal. Precedent method to obtain this product has been at gas phase or at reactive intermediate, and synthesis of ketene is used be done in extreme conditions. Recently found stabilized ketenyl anions become easier to prepare compared to precedent synthetic procedure. A major feature about stabilized ketene is that it can be prepared from carbon monoxide (CO) reacting with main-group starting materials such as ylides, silylene, and phosphinidene to synthesize and isolate for further steps. As CO becomes a more common carbon source for various type of synthesis, this recent finding about stabilizing ketene with main-group elements opens a variety of synthetic routes to target desired products.

<span class="mw-page-title-main">Stibinidene</span> Stibinidene (Chemistry)

Stibinidenes are a class of organoantimony compounds in which the antimony center exhibits a formal oxidation state of +1. The parent stibinidenes have the formula R–Sb, with the antimony center possessing two lone pairs of electrons and a vacant 5p orbital. Reflecting their unusual low coordination number]] at [antimony]], stibinidines cannot be isolated. Instead, their oligomers or their adducts are often robust.

Biradicaloids or diradicaloids are molecules with two radical electrons that have significant interaction with each other. The two unpaired electrons are coupled and can either form a singlet ground state or a triplet ground state.

References

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  7. ↑ Krachko, Tetiana; Bispinghoff, Mark; Tondreau, Aaron M.; Stein, Daniel; Baker, Matthew; Ehlers, Andreas W.; Slootweg, J. Chris; Grützmacher, Hansjörg (2017). "Facile Phenylphosphinidene Transfer Reactions from Carbene–Phosphinidene Zinc Complexes". Angewandte Chemie International Edition. 56 (27): 7948–7951. doi:10.1002/anie.201703672. hdl: 11245.1/4fe684ed-b624-415c-8873-4a6e9114f66b . ISSN   1521-3773. PMID   28505382.
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  14. 1 2 Marinetti, Angela; Mathey, François; Fischer, Jean; Mitschler, André (1982-01-01). "Stabilization of 7-phosphanorbornadienes by complexation; X-ray crystal structure of 2,3-bis(methoxycarbonyl)-5,6-dimethyl-7-phenyl-7-phosphanorbornadiene(pentacarbonyl)-chromium". Journal of the Chemical Society, Chemical Communications (12): 667–668. doi:10.1039/C39820000667. ISSN   0022-4936.
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  22. ↑ Huttner, Gottfried; Knoll, Konrad (1987). "RP-Bridged Metal Carbonyl Clusters: Synthesis, Properties, and Reactions". Angewandte Chemie International Edition in English. 26 (8): 743–760. doi:10.1002/anie.198707431.
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