Phosphinidene: Difference between revisions
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[[File:Phosphinidene.png|thumb|General structure of a phosphinidene|179x179px]] |
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In chemistry '''phosphinidenes''' (IUPAC: '''phosphanylidenes''', or in older chemistry '''phosphinediyls''') are the phosphorus analogs of [[carbene]]s and [[nitrene]]s, having the general structure RP.<ref>{{GoldBookRef|title=phosphanylidenes|file=P04549}}</ref> The name originated from the parent compound, '''phosphinidene''' (HP).<ref>{{Cite journal| doi = 10.1002/anie.200905689| pmid = 20157897| year = 2010| last1 = Aktaş | first1 = H.| last2 = Slootweg | first2 = J.| last3 = Lammertsma | first3 = K.| title = Nucleophilic Phosphinidene Complexes: Access and Applicability| journal = Angewandte Chemie International Edition in English| pages = 2102–2113| volume = 49| issue = 12 }}</ref> They can exist in either a [[singlet state]] or [[triplet state]], with the triplet state being lower in energy. |
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'''Phosphinidenes''' (IUPAC: '''phosphanylidenes''', formerly '''phosphinediyls''') are low-valent phosphorus compounds analogous to [[carbene]]s and [[nitrene]]s, having the general structure RP.<ref name=":0">{{GoldBookRef|title=phosphanylidenes|file=P04549}}</ref><ref name=":2">{{Citation|last=Lammertsma|first=Koop|title=Phosphinidenes|date=2003|url=https://doi.org/10.1007/b11152|work=New Aspects in Phosphorus Chemistry III|pages=95–119|editor-last=Majoral|editor-first=Jean-Pierre|series=Topics in Current Chemistry|place=Berlin, Heidelberg|publisher=Springer|language=en|doi=10.1007/b11152|isbn=978-3-540-36551-8|access-date=2020-11-02}}</ref> The "free" form of these compounds is conventionally described as having a singly-coordinated phosphorus atom containing only 6 electrons in its valence level.<ref name=":2" /> Most phosphinidenes are highly reactive and short-lived, thereby complicating empirical studies on their chemical properties.<ref name=":1">{{cite journal|last1=Liu|first1=Liu|last2=Ruiz|first2=David A.|last3=Munz|first3=Dominik|last4=Bertrand|first4=Guy|year=2016|title=A Singlet Phosphinidene Stable at Room Temperature|journal=Chem|volume=1|page=147-153|doi=10.1016/j.chempr.2016.04.001|doi-access=free}}</ref><ref name=":3">{{Cite journal|last=Nguyen|first=Minh Tho|last2=Van Keer|first2=Annik|last3=Vanquickenborne|first3=Luc G.|date=1996|title=In Search of Singlet Phosphinidenes|url=https://pubs.acs.org/doi/pdf/10.1021/jo9604393|journal=The Journal of Organic Chemistry|volume=61|issue=20|pages=7077–7084|doi=10.1021/jo9604393|issn=0022-3263|via=}}</ref> In the last few decades, several strategies have been employed to stabilize phosphinidenes (e.g. π-donation, [[Steric effects|steric protection]], transition metal complexation),<ref name=":2" /><ref name=":1" /> and researchers have developed a number of reagents and systems that can generate and transfer phosphinidenes as reactive intermediates in the synthesis of various organophosphorus compounds.<ref name=":7">{{Cite journal|last=Transue|first=Wesley J.|last2=Velian|first2=Alexandra|last3=Nava|first3=Matthew|last4=García-Iriepa|first4=Cristina|last5=Temprado|first5=Manuel|last6=Cummins|first6=Christopher C.|date=2017-08-09|title=Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds|url=https://doi.org/10.1021/jacs.7b05464|journal=Journal of the American Chemical Society|volume=139|issue=31|pages=10822–10831|doi=10.1021/jacs.7b05464|issn=0002-7863}}</ref><ref>{{Cite journal|last=Hansen|first=Kerstin|last2=Szilvási|first2=Tibor|last3=Blom|first3=Burgert|last4=Inoue|first4=Shigeyoshi|last5=Epping|first5=Jan|last6=Driess|first6=Matthias|date=2013-08-14|title=A Fragile Zwitterionic Phosphasilene as a Transfer Agent of the Elusive Parent Phosphinidene (:PH)|url=https://doi.org/10.1021/ja4072699|journal=Journal of the American Chemical Society|volume=135|issue=32|pages=11795–11798|doi=10.1021/ja4072699|issn=0002-7863}}</ref><ref>{{Cite journal|last=Krachko|first=Tetiana|last2=Bispinghoff|first2=Mark|last3=Tondreau|first3=Aaron M.|last4=Stein|first4=Daniel|last5=Baker|first5=Matthew|last6=Ehlers|first6=Andreas W.|last7=Slootweg|first7=J. Chris|last8=Grützmacher|first8=Hansjörg|date=2017|title=Facile Phenylphosphinidene Transfer Reactions from Carbene–Phosphinidene Zinc Complexes|url=https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201703672|journal=Angewandte Chemie International Edition|language=en|volume=56|issue=27|pages=7948–7951|doi=10.1002/anie.201703672|issn=1521-3773}}</ref><ref>{{Cite journal|last=Pagano|first=Justin K.|last2=Ackley|first2=Brandon J.|last3=Waterman|first3=Rory|date=2018-02-21|title=Evidence for Iron-Catalyzed α-Phosphinidene Elimination with Phenylphosphine|url=https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.201704954|journal=Chemistry – A European Journal|volume=24|issue=11|pages=2554–2557|doi=10.1002/chem.201704954|issn=0947-6539}}</ref> |
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== Electronic Structure == |
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Like carbenes, phosphinidenes can exist in either a [[singlet state]] or [[triplet state]], with the triplet state typically being more stable.<ref name=":2" /><ref name=":3" /> The stability of these states and their relative energy difference (the singlet-triplet energy gap) is dependent on the substituents. [[File:Phosphinidene singlet triplet.png|thumb|Singlet and Triplet Phosphinidenes|left|286x286px]]The ground state in the parent phosphinidene (PH) is a triplet that is 22 kcal/mol more stable than the lowest singlet state.<ref name=":2" /><ref>{{Cite journal|last=Benkő|first=Zoltán|last2=Streubel|first2=Rainer|last3=Nyulászi|first3=László|date=2006-09-11|title=Stability of phosphinidenes—Are they synthetically accessible?|url=https://pubs.rsc.org/en/content/articlelanding/2006/dt/b608276a|journal=Dalton Transactions|language=en|issue=36|pages=4321–4327|doi=10.1039/B608276A|issn=1477-9234}}</ref> This singlet-triplet energy gap is considerably larger than that of the simplest carbene [[Methylene (compound)|methylene]] (9 kcal/mol).<ref>{{Cite journal|last=Gronert|first=Scott|last2=Keeffe|first2=James R.|last3=More O’Ferrall|first3=Rory A.|date=2011-03-16|title=Stabilities of Carbenes: Independent Measures for Singlets and Triplets|url=https://doi.org/10.1021/ja1071493|journal=Journal of the American Chemical Society|volume=133|issue=10|pages=3381–3389|doi=10.1021/ja1071493|issn=0002-7863}}</ref> |
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[[Ab initio quantum chemistry methods|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]] effect that stabilizes the triplet more than the singlet.<ref name=":3" /> Substituents containing lone pairs (e.g. -NX<sub>2</sub>, -OX, -PX<sub>2</sub> ,-SX) were found to 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.<ref name=":3" /> 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.<ref name=":3" /> |
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==Monomeric phosphinidines== |
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Using very bulky substituents, a phosphinidine has been isolated at room temperature. With the formula R2P-P, the compound reacts with isocyanides and alkenes to give stable adducts.<ref>{{cite journal|last1=Liu|first1=Liu|last2=Ruiz|first2=David A.|last3=Munz|first3=Dominik|last4=Bertrand|first4=Guy|title=A Singlet Phosphinidene Stable at Room Temperature|journal=Chem |year=2016|volume=1|page=147-153|doi=10.1016/j.chempr.2016.04.001|doi-access=free}}</ref> |
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==Stable Monomeric Phosphino-Phosphinidene== |
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[[Guy Bertrand (chemist)|Bertrand]] and coworkers synthesized a stable singlet phosphino-phosphinidene compound using extremely bulky substituents.<ref name=":1" /> Hitherto, there had been no free singlet phosphinidenes that were characterized by [[spectroscopy]].<ref name=":1" /> 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.<ref name=":1" /> <sup>31</sup>P [[nuclear magnetic resonance spectroscopy|NMR spectroscopy]] shows assigned product peaks at 80.2 and -200.4 ppm, with a [[J-coupling]] constant of J<sub>PP</sub> = 883.7 Hz. The very high P-P coupling constant is indicative of P-P multiple bond character.<ref name=":1" /> The air/water sensitivity and high solubility of this compound prevented characterization by [[X-ray crystallography|X-ray crystallography.]]<ref name=":1" /> [[File:Stable phosphinidene1.png|thumb|434x434px|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.<ref name=":1" /> |center]] |
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Terminal transition-metal-complexed phosphinidenes L<sub>n</sub>M=P-R are phosphorus analogs of [[transition metal carbene complexes]] where L is a spectator [[ligand]]. Two examples of this group are [(OC)<sub>5</sub>W=P-Ph]<ref>{{Cite journal| doi = 10.1021/ja00380a029| title = Generation and trapping of terminal phosphinidene complexes. Synthesis and x-ray crystal structure of stable phosphirene complexes| year = 1982| last1 = Marinetti | first1 = A.| last2 = Mathey | first2 = F.| last3 = Fischer | first3 = J.| last4 = Mitschler | first4 = A.| journal = Journal of the American Chemical Society| volume = 104| issue = 16| pages = 4484 }}</ref> and Cp<sub>2</sub>W=P-Mes*.<ref>{{Cite journal| doi = 10.1039/C39870001282| title = The first stable transition metal (molybdenum or tungsten) complexes having a metal?phosphorus(III) double bond: the phosphorus analogues of metal aryl- and alkyl-imides; X-ray structure of [Mo(?-C5H5)2(?PAr)](Ar = C6H2But 3-2,4,6)| year = 1987| last1 = Hitchcock | first1 = P. B.| last2 = Lappert | first2 = M. F.| last3 = Leung | first3 = W. P.| journal = Journal of the Chemical Society, Chemical Communications| issue = 17| pages = 1282 }}</ref> |
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[[Density functional theory]] and [[Natural bond orbital|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.<ref name=":1" /> 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.<ref name=":1" /> Inspection of the outputted wavefunctions shows that the [[HOMO and LUMO|HOMO]] and HOMO-1 are P-P π-bonding orbitals and the [[HOMO and LUMO|LUMO]] is a P-P π*-antibonding orbital.<ref name=":1" /> Further evidence of multiple bond character between the phosphorus atoms was provided by natural resonance theory and a large [[Kenneth B. Wiberg|Wiberg]] bond index (P<sub>1</sub>-P<sub>2</sub>: 2.34).<ref name=":1" /> 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).<ref name=":1" /> |
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[[File:Bertrand phosphinidene HOMO-LUMO.png|center|thumb|550x550px|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<ref name=":1" /> with NBO 6.0 in [[ORCA (quantum chemistry program)|ORCA. 4.2.0]] and visualized in IBOview. ]] |
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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<ref name=":1" /><ref name=":5">{{Cite journal|last=Hansmann|first=Max M.|last2=Jazzar|first2=Rodolphe|last3=Bertrand|first3=Guy|date=2016-06-30|title=Singlet (Phosphino)phosphinidenes are Electrophilic|url=https://pubs.acs.org/doi/10.1021/jacs.6b04232|journal=Journal of the American Chemical Society|language=EN|volume=138|issue=27|pages=8356–8359|doi=10.1021/jacs.6b04232|issn=0002-7863}}</ref> 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.<ref name=":5" /> |
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[[File:Reactivity of phosphinidene.png|center|thumb|459x459px|Reactivity of phosphino-phosphinidene with various nucleophiles<ref name=":1" /><ref name=":5" />]] |
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== Phospha-Wittig Fragmentation == |
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[[File:Phosphawittig.png|thumb|498x498px|Dominant resonance structures of the phospha-Wittig reagent from Fritz et al.<ref name=":4">{{Cite journal|last=Fritz|first=Gerhard|last2=Vaahs|first2=Tilo|last3=Fleischer|first3=Holm|last4=Matern|first4=Eberhard|date=1989|title=tBu2PPPbrtBu2. LiBr and the Formation of tBu2P|url=https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.198903151|journal=Angewandte Chemie International Edition in English|volume=28|issue=3|pages=315–316|doi=10.1002/anie.198903151|issn=1521-3773}}</ref> ]] |
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In 1989, Fritz et al. synthesized the phospha-Wittig species shown to the right.<ref name=":4">{{Cite journal|last=Fritz|first=Gerhard|last2=Vaahs|first2=Tilo|last3=Fleischer|first3=Holm|last4=Matern|first4=Eberhard|date=1989|title=tBu2PPPbrtBu2. LiBr and the Formation of tBu2P|url=https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.198903151|journal=Angewandte Chemie International Edition in English|volume=28|issue=3|pages=315–316|doi=10.1002/anie.198903151|issn=1521-3773}}</ref> 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 [[Zwitterion|zwitterionic]] form) that are analogous to those of the [[Ylide|phosphonium ylides]] that are used in the [[Wittig reaction]]. |
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Fritz et al. found that this particular phospha-Wittig reagent thermally decomposes at 20 °C to give <sup>t</sup>Bu<sub>2</sub>PBr, LiBr, and cyclophosphanes.<ref name=":4" /> The authors proposed that the singlet phosphino-phosphinidene <sup>t</sup>Bu<sub>2</sub>PP 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.<ref name=":4" /> [[File:Phosphawittig reactions.png|center|thumb|662x662px|Reactivity of the phopha-Wittig reagent as described in Fritz et al.<ref name=":4">{{Cite journal|last=Fritz|first=Gerhard|last2=Vaahs|first2=Tilo|last3=Fleischer|first3=Holm|last4=Matern|first4=Eberhard|date=1989|title=tBu2PPPbrtBu2. LiBr and the Formation of tBu2P|url=https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.198903151|journal=Angewandte Chemie International Edition in English|volume=28|issue=3|pages=315–316|doi=10.1002/anie.198903151|issn=1521-3773}}</ref>]] |
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⚫ | More common than complexes of terminal |
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Terminal transition-metal-complexed phosphinidenes L<sub>n</sub>M=P-R are phosphorus analogs of [[transition metal carbene complexes]] where L is a spectator [[ligand]]. The first terminal phosphinidene complex was reported by Marinetti et al., who observed the formation of the transient species [(OC)<sub>5</sub>M=P-Ph] during the fragmentation of 7-phosphanorbornadiene [[molybdenum]] and [[tungsten]] complexes inside a [[Mass spectrometry|mass spectrometer]].<ref name="Marinetti>{{Cite journal|last=Marinetti|first=Angela|last2=Mathey|first2=François|last3=Fischer|first3=Jean|last4=Mitschler|first4=André|date=1982-01-01|title=Stabilization of 7-phosphanorbornadienes by complexation; X-ray crystal structure of 2,3-bis(methoxycarbonyl)-5,6-dimethyl-7-phenyl-7-phosphanorbornadiene(pentacarbonyl)-chromium|url=https://pubs.rsc.org/en/content/articlelanding/1982/c3/c39820000667|journal=Journal of the Chemical Society, Chemical Communications|language=en|issue=12|pages=667–668|doi=10.1039/C39820000667|issn=0022-4936}}</ref><ref name="Mathey">{{Cite journal|last=Mathey|first=François|date=1987|title=The Development of a Carbene-like Chemistry with Terminal Phosphinidene Complexes|url=https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.198702753|journal=Angewandte Chemie International Edition in English|language=en|volume=26|issue=4|pages=275–286|doi=10.1002/anie.198702753|issn=1521-3773}}</ref> Soon after, they discovered that these 7-phosphanorbornadiene complexes could be used to transfer the phosphinidene complex [(OC)<sub>5</sub>M=P-R] to various unsaturated substrates.<ref name="Mathey" /><ref name="Marinetti2>{{Cite journal|last=Marinetti|first=Angela|last2=Mathey|first2=Francois|last3=Fischer|first3=Jean|last4=Mitschler|first4=Andre|date=1982-08-01|title=Generation and trapping of terminal phosphinidene complexes. Synthesis and x-ray crystal structure of stable phosphirene complexes|url=https://doi.org/10.1021/ja00380a029|journal=Journal of the American Chemical Society|volume=104|issue=16|pages=4484–4485|doi=10.1021/ja00380a029|issn=0002-7863}}</ref> |
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[[File:7-phosphanorbornadiene synthesis and reaction.png|center|thumb|785x785px|Synthesis and reactivity of several 7-phosphanorbornadiene complexes<ref name="Marinetti" /><ref name="Mathey" /><ref name="Marinetti2" /> ]] |
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[[Michael F. Lappert|Lappert]] and coworkers reported the first synthesis of a stable terminal phosphinidene complex: lithium metallocene hydrides [Cp<sub>2</sub>MHLi]<sub>4</sub> of Mo and W were reacted with aryl-dichlorophosphines RPCl<sub>2</sub> to yield Cp<sub>2</sub>M=P-R, which were able to be characterized by [[X-ray crystallography|single crystal X-ray diffraction.]]<ref name="Lappert">{{Cite journal|last=Hitchcock|first=Peter B.|last2=Lappert|first2=Michael F.|last3=Leung|first3=Wing-Por|date=1987-01-01|title=The first stable transition metal (molybdenum or tungsten) complexes having a metal–phosphorus(III) double bond: the phosphorus analogues of metal aryl- and alkyl-imides; X-ray structure of [Mo(η-C5H5)2(PAr)](Ar = C6H2But3-2,4,6)|url=https://pubs.rsc.org/en/content/articlelanding/1987/c3/c39870001282|journal=Journal of the Chemical Society, Chemical Communications|language=en|issue=17|pages=1282–1283|doi=10.1039/C39870001282|issn=0022-4936}}</ref> |
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[[File:Lappert metallocene phosphinidene.png|center|thumb|299x299px|Lappert and coworkers' synthesis of first stable terminal phosphinidene complex<ref name="Lappert" />]] |
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⚫ | More common than complexes of terminal phosphinidene ligands are [[cluster compound]]s wherein the phosphinidene is a triply and less commonly doubly [[bridging ligand]]. One example is the ter-butylphosphinidene complex (t-BuP)Fe<sub>3</sub>(CO)<sub>10</sub>.<ref>{{cite journal|doi=10.1002/anie.198707431|title=RP-Bridged Metal Carbonyl Clusters: Synthesis, Properties, and Reactions|journal=Angewandte Chemie International Edition in English|volume=26|issue=8|pages=743–760|year=1987|last1=Huttner|first1=Gottfried|last2=Knoll|first2=Konrad}}</ref> |
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== Dibenzo-7-phosphanorbornadiene derivatives == |
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A class of RPA (A = anthracene) compounds were developed and explored by [[Christopher C. Cummins|Cummins]] and coworkers.<ref name=":6">{{Cite journal|last=Velian|first=Alexandra|last2=Cummins|first2=Christopher C.|date=2012-08-20|title=Facile Synthesis of Dibenzo-7λ3-phosphanorbornadiene Derivatives Using Magnesium Anthracene|url=https://pubs.acs.org/doi/pdf/10.1021/ja306902j|journal=Journal of the American Chemical Society|volume=134|issue=34|pages=13978–13981|doi=10.1021/ja306902j|issn=0002-7863}}</ref> |
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Treatment of a bulky phosphine chloride (RPCl<sub>2</sub>) with [[magnesium anthracene]] affords a dibenzo-7-phosphanorbornadiene compound (RPA).<ref name=":6" /> Under thermal conditions, the RPA compound (R = NiPr<sub>2</sub>) decomposes to yield anthracene; kinetic experiments found this decomposition to be first-order.<ref name=":6" /> It was hypothesized that the amino-phosphinidene iPr<sub>2</sub>NP is formed as a transient intermediate species, and this was corroborated by an experiment where [[Cyclohexa-1,3-diene|1,3-cyclohexadiene]] was used as a trapping agent, forming ''anti''-iPr<sub>2</sub>NP(C<sub>6</sub>H<sub>8</sub>).<ref name=":6" /> |
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[[File:RPA reaction.png|center|thumb|824x824px|Synthesis of RPA (R = NiPr<sub>2</sub>) and an example phosphinidene transfer reaction with 1,3-cyclohexadiene<ref name=":6" />]] |
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[[Mass spectrometry|Molecular beam mass spectrometry]] has enabled the detection of the evolution of amino-phosphinidene fragments from a number of alkylamide derivatives (e.g. Me<sub>2</sub>NP+ and Me<sub>2</sub>NPH+ from Me<sub>2</sub>NPA) in the gas-phase at elevated temperatures.<ref name=":7" /> |
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==See also== |
==See also== |
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* [[Carbene analog]] |
* [[Carbene analog]] |
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*[[:Category:Phosphorus compounds|Phosphorus compounds]] |
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==References== |
==References== |
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{{Reflist}} |
{{Reflist}} |
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[[Category:Reactive intermediates]] |
[[Category:Reactive intermediates]] |
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[[Category:Organophosphorus compounds]] |
[[Category:Organophosphorus compounds]] |
Revision as of 23:09, 2 December 2020
Phosphinidenes (IUPAC: phosphanylidenes, formerly phosphinediyls) are low-valent phosphorus compounds analogous to carbenes and nitrenes, having the general structure RP.[1][2] The "free" form of these compounds is conventionally described as having a singly-coordinated phosphorus atom containing 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] In the last few decades, several strategies have been employed to stabilize phosphinidenes (e.g. π-donation, steric protection, transition metal complexation),[2][3] and researchers have developed a number of reagents and systems that can generate and transfer phosphinidenes as reactive intermediates in the synthesis of various organophosphorus compounds.[5][6][7][8]
Electronic Structure
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) is dependent 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 effect that stabilizes the triplet more than the singlet.[4] Substituents containing lone pairs (e.g. -NX2, -OX, -PX2 ,-SX) were found to 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]
Stable Monomeric Phosphino-Phosphinidene
Bertrand and coworkers synthesized a stable singlet phosphino-phosphinidene compound using extremely bulky substituents.[3] Hitherto, there had been no free singlet phosphinidenes that were characterized by spectroscopy.[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]
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]
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][11] 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.[11]
Phospha-Wittig Fragmentation
In 1989, Fritz et al. synthesized the phospha-Wittig species shown to the right.[12] 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.[12] 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.[12]
Phosphinidene complexes
Terminal transition-metal-complexed phosphinidenes LnM=P-R are phosphorus analogs of transition metal carbene complexes where L is a spectator ligand. The first terminal phosphinidene complex was reported by Marinetti et al., who observed the formation of the transient species [(OC)5M=P-Ph] during the fragmentation of 7-phosphanorbornadiene molybdenum and tungsten complexes inside a mass spectrometer.[13][14] 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.[14][15]
Lappert and coworkers reported the first synthesis of a stable terminal phosphinidene complex: lithium metallocene hydrides [Cp2MHLi]4 of Mo and W were reacted with aryl-dichlorophosphines RPCl2 to yield Cp2M=P-R, which were able to be characterized by single crystal X-ray diffraction.[16]
More common than complexes of terminal phosphinidene ligands are cluster compounds wherein the phosphinidene is a triply and less commonly doubly bridging ligand. One example is the ter-butylphosphinidene complex (t-BuP)Fe3(CO)10.[17]
Dibenzo-7-phosphanorbornadiene derivatives
A class of RPA (A = anthracene) compounds were developed and explored by Cummins and coworkers.[18]
Treatment of a bulky phosphine chloride (RPCl2) with magnesium anthracene affords a dibenzo-7-phosphanorbornadiene compound (RPA).[18] Under thermal conditions, the RPA compound (R = NiPr2) decomposes to yield anthracene; kinetic experiments found this decomposition to be first-order.[18] 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).[18]
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]
See also
References
- ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "phosphanylidenes". doi:10.1351/goldbook.P04549
- ^ a b c d e Lammertsma, Koop (2003), Majoral, Jean-Pierre (ed.), "Phosphinidenes", New Aspects in Phosphorus Chemistry III, Topics in Current Chemistry, Berlin, Heidelberg: Springer, pp. 95–119, doi:10.1007/b11152, ISBN 978-3-540-36551-8, retrieved 2020-11-02
- ^ a b c d e f g h i j k l m n o p Liu, Liu; Ruiz, David A.; Munz, Dominik; Bertrand, Guy (2016). "A Singlet Phosphinidene Stable at Room Temperature". Chem. 1: 147-153. doi:10.1016/j.chempr.2016.04.001.
- ^ a b c d e Nguyen, Minh Tho; Van Keer, Annik; Vanquickenborne, Luc G. (1996). "In Search of Singlet Phosphinidenes". The Journal of Organic Chemistry. 61 (20): 7077–7084. doi:10.1021/jo9604393. ISSN 0022-3263.
- ^ a b Transue, Wesley J.; Velian, Alexandra; Nava, Matthew; García-Iriepa, Cristina; Temprado, Manuel; Cummins, Christopher C. (2017-08-09). "Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds". Journal of the American Chemical Society. 139 (31): 10822–10831. doi:10.1021/jacs.7b05464. ISSN 0002-7863.
- ^ Hansen, Kerstin; Szilvási, Tibor; Blom, Burgert; Inoue, Shigeyoshi; Epping, Jan; Driess, Matthias (2013-08-14). "A Fragile Zwitterionic Phosphasilene as a Transfer Agent of the Elusive Parent Phosphinidene (:PH)". Journal of the American Chemical Society. 135 (32): 11795–11798. doi:10.1021/ja4072699. ISSN 0002-7863.
- ^ 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. ISSN 1521-3773.
- ^ Pagano, Justin K.; Ackley, Brandon J.; Waterman, Rory (2018-02-21). "Evidence for Iron-Catalyzed α-Phosphinidene Elimination with Phenylphosphine". Chemistry – A European Journal. 24 (11): 2554–2557. doi:10.1002/chem.201704954. ISSN 0947-6539.
- ^ Benkő, Zoltán; Streubel, Rainer; Nyulászi, László (2006-09-11). "Stability of phosphinidenes—Are they synthetically accessible?". Dalton Transactions (36): 4321–4327. doi:10.1039/B608276A. ISSN 1477-9234.
- ^ Gronert, Scott; Keeffe, James R.; More O’Ferrall, Rory A. (2011-03-16). "Stabilities of Carbenes: Independent Measures for Singlets and Triplets". Journal of the American Chemical Society. 133 (10): 3381–3389. doi:10.1021/ja1071493. ISSN 0002-7863.
- ^ a b c Hansmann, Max M.; Jazzar, Rodolphe; Bertrand, Guy (2016-06-30). "Singlet (Phosphino)phosphinidenes are Electrophilic". Journal of the American Chemical Society. 138 (27): 8356–8359. doi:10.1021/jacs.6b04232. ISSN 0002-7863.
- ^ a b c d e Fritz, Gerhard; Vaahs, Tilo; Fleischer, Holm; Matern, Eberhard (1989). "tBu2PPPbrtBu2. LiBr and the Formation of tBu2P". Angewandte Chemie International Edition in English. 28 (3): 315–316. doi:10.1002/anie.198903151. ISSN 1521-3773.
- ^ a b 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.
- ^ a b c Mathey, François (1987). "The Development of a Carbene-like Chemistry with Terminal Phosphinidene Complexes". Angewandte Chemie International Edition in English. 26 (4): 275–286. doi:10.1002/anie.198702753. ISSN 1521-3773.
- ^ a b Marinetti, Angela; Mathey, Francois; Fischer, Jean; Mitschler, Andre (1982-08-01). "Generation and trapping of terminal phosphinidene complexes. Synthesis and x-ray crystal structure of stable phosphirene complexes". Journal of the American Chemical Society. 104 (16): 4484–4485. doi:10.1021/ja00380a029. ISSN 0002-7863.
- ^ a b Hitchcock, Peter B.; Lappert, Michael F.; Leung, Wing-Por (1987-01-01). "The first stable transition metal (molybdenum or tungsten) complexes having a metal–phosphorus(III) double bond: the phosphorus analogues of metal aryl- and alkyl-imides; X-ray structure of [Mo(η-C5H5)2(PAr)](Ar = C6H2But3-2,4,6)". Journal of the Chemical Society, Chemical Communications (17): 1282–1283. doi:10.1039/C39870001282. ISSN 0022-4936.
- ^ 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.
- ^ a b c d e Velian, Alexandra; Cummins, Christopher C. (2012-08-20). "Facile Synthesis of Dibenzo-7λ3-phosphanorbornadiene Derivatives Using Magnesium Anthracene". Journal of the American Chemical Society. 134 (34): 13978–13981. doi:10.1021/ja306902j. ISSN 0002-7863.