Isolation of some sterically protected unsymmetrical diphosphenes: nature of the phosphorus-phosphorus double bond

Yoshifuji, Masaaki; Shibayama, Katsuhiro; Inamoto, Naoki; Matsushita, Toshio; Nishimoto, Kichisuke

doi:10.1021/ja00346a077

Cited by 151 publications

(36 citation statements)

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“…A small number of achiral, air-stable primary phosphines have been reported (Fig. 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].…”

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“…In solution, the naphthylphosphines 12 and 13 show similar levels of oxidation, with notable quantities of both 4 ]; we then adopted the same protocol to gain an insight into the net electron donor nature of the above primary phosphines. An inspection of entries 4 and 8 in Table 1.1 show that both the air-stable (S)-6 and the reactive phenylphosphine 15 gave the same v (CO) (A 1 ) stretching frequency.…”

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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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The Primary Phosphine Renaissance

Higham¹

2011

Phosphorus Compounds

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“…Appel's scheme [12] was used for generating 1,4-diphospha-1,3-butadienes. The 2,4-di-tert-butyl-6-methylphenyl group, which allows stabilization of diphosphenes [14], phosphaalkenes [15], dithiophosphorane [16], and arsaalkenes [17], as well as the 1,4-diphospha-1,3-butadienes with a rigid cyclobutene backbone [18], was employed as a protection group. 2,4-Di-tert-butyl-6-methylphenyllithium (1a) was reacted with 1,2-bis(dichlorophosphino)ethane (2) in a molar ratio of 2:1, followed by the addition of 1,5-diazabicyclo has been found to be unstable at room temperature and it underwent [2+4] cycloaddition to form the dimer 5a.…”

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confidence: 99%

A novel pattern of dimerization for 1, 4‐diphospha‐1,3‐butadienes

Ionkin

Marshall

2003

Heteroatom Chemistry

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“…Because we were unable to obtain the bisphosphaalkene through the use of the 2,4,6-tritert-butylphenyl group at phosphorus, we decided to apply the 2,4-di-tert-butyl-6-methylphenyl group for the protection of a two coordination status for the phosphorus atom. The 2,4-di-tert-butyl-6-methylphenyl group has been shown to allow the stabilization of diphosphenes [15,16], phosphaalkenes [17], dithiophosphoranes [18], and arsaalkenes [19].…”

Section: Resultsmentioning

confidence: 99%