(Ferrocenylmethyl)phosphine, an air-stable primary phosphine

Goodwin, Nicholas J.; Henderson, William; Nicholson, Brian K.; Fawcett, J. Paul; Russell, David R.

doi:10.1039/a901036j

Cited by 65 publications

(81 citation statements)

References 48 publications

(24 reference statements)

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“…1.3) represents the first such characterization of an optically-pure primary phosphine [38,39]. The P-C bond length of 1.811(6) Å correlates with the few other crystal structures reported of uncoordinated primary phosphines [1,[6][7][8][9][10][11]40]. The solid-state nature of (R)-5 prompted us to investigate its sensitivity to aerobic oxygen; after 7 days left standing on the bench in air, no oxidation was evident by 31 P NMR spectroscopy.…”

supporting

confidence: 51%

“…1.4) but these are stabilized on account of high steric hindrance such as supermesityl phosphine 7 [4,5], triptycylphosphine 8 [6] and various related compounds [1], or their stability is not understood. Examples of the latter class are the air-stable ferrocene derivative 9 [7], and the heteroatom-containing diprimary phosphines 10 [9] and 11 [1,2]. For 9, the authors suggest the oxidative resistance may be due to an alkyl spacer group effect, whilst for the latter compounds the presence of the remote heteroatoms are postulated to possibly confer stability via negative hyperconjugation [9,13,14].…”

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confidence: 99%

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The Primary Phosphine Renaissance

Higham¹

2011

Phosphorus Compounds

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Primary phosphines are renowned for being toxic, volatile, pyrophoric compounds which have to be handled under an inert atmosphere due to their ease of air-oxidation. Thus despite numerous potential applications, they remain underutilized precursors in synthetic chemistry. Only a small number of air-stable primary phosphines are known, and their stability is either attributable to high steric hindrance about the phosphino group or the underlying factors are as yet undetermined. This work is an account of the recent studies carried out by our research group and presents a new family of air-stable chiral primary phosphines (R)-5 and (S)-6 based on the binaphthyl backbone. The stabilization is a result of p-conjugation and is discussed with reference to naphthyl-and phenyl-based analogues. Computational studies based on the DFT B3LYP/6-31G* level of theory suggests significant p-conjugation or sufficient heteroatom presence dislocates the phosphorus away from the HOMO of the ground state and raises the energy of the HOMO in the associated radical cation, with a threshold of stability emerging. Novel phosphonites, phospholanes and bis(hydroxymethyl)phosphines were synthesized from (R)-5 and (S)-6 and tested in the catalytic asymmetric hydrosilylation of styrene.

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confidence: 51%

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confidence: 99%

The Primary Phosphine Renaissance

Higham¹

2011

Phosphorus Compounds

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“…[5] Since then, other related ferrocene-derived hydroxymethyl phosphines and their derivatives have been reported [6 -8]; in all of these compounds there is a CH 2 or CHMe spacer between the ferrocenyl group and the phosphine. In this paper we report the synthesis of new ferrocenyl hydroxymethylphosphines where the phosphine group is 4 bonded directly to the cyclopentadienyl ring.…”

Section: Introductionmentioning

confidence: 99%

Ferrocenyl hydroxymethylphosphines (η5-C5H5)Fe[η5-C5H4P(CH2OH)2] and 1,1′-[Fe{η5-C5H4P(CH2OH)2}2] and their chalcogenide derivatives

Henderson

Alley

2002

Journal of Organometallic Chemistry

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“…(Ferrocenylmethyl)phosphane (1) [43] and the complexes [M(cod)(CH 3 )Cl] [M = Pd; Pt] [44] were prepared by literature methods. C and H elemental analyses were carried out with a PerkinElmer 240B CHN Elemental Analyzer.…”

Section: Methodsmentioning

confidence: 99%