Gas-Phase Synthesis and Characterization of an Azaphosphirenium Ion:  The First N,P-Analogue of the Aromatic Cyclopropenyl Cation

Moraes, Luiz Alberto Beraldo; Eberlin, Marcos N.; Laali, Kenneth K.

doi:10.1021/om010458p

Cited by 10 publications

(7 citation statements)

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“…Thus several longlived phosphenium ions R 2 P ϩ were successfully generated and isolated in the gas phase, and their intrinsic reactivity was probed by various MS techniques. 10 We have recently applied multiple-stage MS techniques to form and investigate the intrinsic chemistry of the 3-dimethylamino-1,1-dimethyl-1Hazaphosphiren-1-ium ion (11), the first member of the hitherto unknown class of azaphosphirenium ions and the first N,P-analogue of the aromatic cyclopropenyl cation. 11 Herein we report that long-lived three-membered ring 2-tertbutyl-3-phenylphosphirenylium ions 13 can be formed in abundance in the gas phase from 1-chloro-1H-phosphirene 6 via 70 eV electron ionization.…”

Section: Introductionmentioning

confidence: 99%

“…10 We have recently applied multiple-stage MS techniques to form and investigate the intrinsic chemistry of the 3-dimethylamino-1,1-dimethyl-1Hazaphosphiren-1-ium ion (11), the first member of the hitherto unknown class of azaphosphirenium ions and the first N,P-analogue of the aromatic cyclopropenyl cation. 11 Herein we report that long-lived three-membered ring 2-tertbutyl-3-phenylphosphirenylium ions 13 can be formed in abundance in the gas phase from 1-chloro-1H-phosphirene 6 via 70 eV electron ionization. We have subsequently used collision-induced dissociation (CID) and ion-molecule reactions followed by CID of the major product ions to examine its reactivity towards representative nucleophiles and dienes.…”

Section: Introductionmentioning

confidence: 99%

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Gas phase chemistry of the 2-tert-butyl-3-phenylphosphirenylium cation: novel onium ions by nucleophilic attack at phosphorus and de novo P-spiro bicyclic phosphonium ions via [4 + 2+] cycloaddition with dienes

et al. 2002

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The 2-tert-butyl-3-phenylphosphirenylium ion 13 is formed in abundance in the gas phase from 1-chloro-1H-phosphirene 6 upon 70 eV electron ionization. Collision-induced dissociation (CID) and ion-molecule reactions followed by CID of the product ions were performed via pentaquadrupole mass spectrometry to probe the structure and reactivity of 13 towards representative nucleophiles and dienes. Under CID conditions, 13 produces a variety of fragment ions mainly via dissociation processes that are preceded by isomerizations. In ion-molecule reactions, 13 reacts readily with ethers, sulfides, pyridine and aniline to form hitherto unknown oxonium, sulfonium and azonium ions via nucleophilic attack at phosphorus. With butadiene, isoprene, 1-acetoxybutadiene, and with Danishefsky's diene (1-methoxy-3-silyloxybuta-1,3-diene), 13 undergoes [4 + 2+] cycloaddition at phosphorus to generate novel P-spiro bicyclic phosphonium ions. With butadiene and isoprene, a second [4 + 2] cycloaddition occurs which generates P-spiro tricyclic phosphonium ions. Whereas 13 also reacts readily with 1-acetoxybutadiene via[4 + 2+] cycloaddition, most of the nascent P-spiro cycloadducts are unstable and dissociate by the loss of either a neutral ketene or acetic acid molecule. B3LYP/6-31G(d,p) calculations were performed to gain insight into the structures of the product ions. The present study constitutes the first successful attempt to unravel the chemistry of 13, a unique 2 pi-Hückel phosphirenylium ion for which no direct solution chemical reactivity data are as yet available. The present findings also create a parallel with the solution reactivity of 1-halo-1H-phosphirenes and 1-triflato-1H-phosphirenes as precursors to phosphirenylium ions.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gas phase chemistry of the 2-tert-butyl-3-phenylphosphirenylium cation: novel onium ions by nucleophilic attack at phosphorus and de novo P-spiro bicyclic phosphonium ions via [4 + 2+] cycloaddition with dienes

et al. 2002

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“…Ion/molecule reactions also play an important role in the preparation of elusive ionic species which are not easily accessible in solution or from direct ionization or dissociation of neutral molecules [264][265][266][267][268]. A historic but still remarkable example is the readily preparation of the methionium ion, CH 5 þ , by the gas-phase ion/ molecule reaction of CH 4 þ with CH 4 [269] mentioned above.…”

Section: Synthesis Of Elusive Ionic Speciesmentioning

confidence: 99%

Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

Chen

2009

Reactive Intermediates

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Mass spectrometry (MS), originally developing from nineteenth-century physics, has a history dating back more than a hundred years. Since then, the technique has advanced enormously. The advent of new methods of ion production, novel mass analyzers, and new tools for data processing has made it possible to analyze almost all chemical entities, ranging from small organic compounds to large biological molecules and whole living cells/tissues. Today, mass spectrometry has become one of the most powerful and popular modern physical-chemical methods to study the details of elemental and molecular processes in nature. Because of its unparalleled capability of providing information on molecular weight, chemical structures, isotopic content, and even molecular dynamics, mass spectrometry is playing an increasingly significant role in the chemical and life sciences. As a traditional analytical tool and a booming technology for biomedicine, it has found extensive applications in nearly every discipline involving chemical analysis such as petroleum prospecting and refining, food processing, drug discovery, metablomics, genomics, proteomics and structural biology, as well as the environment, public safety, and industrial process monitoring. Along with the development of mass spectrometric technology, the chemistry of gaseous ions has been explored by the study of unimolecular and collision-induced dissociation (CID) [1][2][3][4] and by the study of ion/molecule reactions [2,[5][6][7][8][9][10][11][12][13][14][15][16][17] and ion/ion reactions [18][19][20][21][22][23][24][25][26] in the gas phase. The study of gas-phase ion chemistry has both fundamental and practical significance because it not only provides diverse information on ion reactivity, thermochemistry, and dynamics, but it also forms one basis for chemical analysis using mass spectrometry. In addition, the ion reactivity examined in the isolated gas-phase environment of mass spectrometers has a strong connection with reaction chemistry in solution, as well as contrasting with it. Many important ionic intermediates which are hard to probe in the condensed phase can be easily accessed in the gas phase. Therefore, mass spectrometry has also become an important and unique tool for the mechanistic investigation of organic reactions (particularly organometallic reactions), since soft electrospray ionization (ESI) technology [27, 28] became available. In this regard, there is a large body of work in the literature, which is reviewed in this book. j37This chapter will provide an overview of the history and the current state of the art of mass spectrometry-based study of ion chemistry, specifically of ion/molecule reactions. As this is a broad topic with an immense literature (over 15 000 papers), our emphasis will be placed on the applications of ESI-MS coupled with gas-phase ion/ molecule reactions and tandem mass spectrometry in organometallic chemistry, including probing key intermediates and reaction pathways of organometallic reactions in solution. We will start with...

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“…(47)]. 204 DFT calculations predict that the phosphavinyl cation 90 undergoes rapid cyclization to form the 3-(dimethylamino)-1,1-dimethyl-1H-azaphosphirenium cation 91. This species was investigated via CID and ion-molecule reactions with N, O, P and S nucleophiles, as well as isoprene.…”

Section: Reactions Of Organic Ions Containing Heteroatomsmentioning

confidence: 99%

9 Organic gas phase ion chemistry

Waters

O’Hair

2002

Annu. Rep. Prog. Chem., Sect. B: Org. Chem.

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Gas-Phase Synthesis and Characterization of an Azaphosphirenium Ion: The First N,P-Analogue of the Aromatic Cyclopropenyl Cation

Cited by 10 publications

References 30 publications

Gas phase chemistry of the 2-tert-butyl-3-phenylphosphirenylium cation: novel onium ions by nucleophilic attack at phosphorus and de novo P-spiro bicyclic phosphonium ions via [4 + 2+] cycloaddition with dienes

Gas phase chemistry of the 2-tert-butyl-3-phenylphosphirenylium cation: novel onium ions by nucleophilic attack at phosphorus and de novo P-spiro bicyclic phosphonium ions via [4 + 2+] cycloaddition with dienes

Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

9 Organic gas phase ion chemistry

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