Synthesis and multinuclear NMR characterization of iminophosphoranyl phosphines and silanes

Goumri, Stéphanie; Lacassin, Francis; Baceiredo, Antoine; Bertrand, Guy

doi:10.1002/(sici)1098-1071(199611)7:6<403::aid-hc1>3.0.co;2-9

Cited by 5 publications

(3 citation statements)

References 18 publications

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“…Recently, using pure cis and trans monodeuterated styrene isomers, 147b we have observed the stereospecific formation of the corresponding cyclopropanes 62(cis) and 62(trans), respectively (Scheme 10). 148 The concerted nature of the cyclopropanation reactions has been corroborated by the results observed by reacting XIa,f with a variety of carbon-heteroatom double and triple bonds (see sections V.3.2 and V.3.3).…”

Section: V31 Addition To Carbon−carbon Double Bondsmentioning

confidence: 68%

“…147a In fact, carbenes XIa,f undergo cyclopropanation reactions with a variety of monosubstituted electronpoor alkenes such as methyl acrylate, 135 alkyl-substituted olefins or styrene derivatives. 148 All these reactions occur at room temperature, and the corresponding cyclopropanes 57a,f-61a,f are obtained in high yields (Scheme 9).…”

Section: V31 Addition To Carbon−carbon Double Bondsmentioning

confidence: 99%

“…The NMR data for 57a,f-61a,f are consistent with a "syn-attack" 149 of the phosphinocarbenes XIa,f, and this has been confirmed by a single-crystal X-ray diffraction study of 58f. 148 So far, this stereoselectivity is not well understood, especially since steric effects should favor a "trans attack" [the bis(amino)phosphino group being more sterically demanding than the trimethylsilyl group].…”

Section: V31 Addition To Carbon−carbon Double Bondsmentioning

confidence: 99%

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Stable Carbenes

et al. 1999

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Section: V31 Addition To Carbon−carbon Double Bondsmentioning

confidence: 68%

Section: V31 Addition To Carbon−carbon Double Bondsmentioning

confidence: 99%

Section: V31 Addition To Carbon−carbon Double Bondsmentioning

confidence: 99%

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Effective Control of the Electron‐donating Ability of Phosphines by using Phosphazenyl and Phosphoniumylidyl Substituents

Werra

Wünsche

Rathmann

et al. 2020

Zeitschrift anorg allge chemie

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Phosphoniumylidyl and phosphazenyl groups are effective substituents to increase the electron‐donating ability of tertiary phosphines. However, the influence of structural variations among those substituents on the electronic properties of the phosphines is little explored. Herein, we show that protonation of the ylidic carbon atom of phosphoniumylidyl phosphines increases the Tolman electronic parameter (TEP) by ΔTEP = 16.0–18.8 cm–1. Furthermore, phosphazenyl phosphines were synthesized with isopropyl groups (NP{iPr}3) and tetramethylguanidino groups (NP{tmg}3) at the phosphonium center. Determination of their TEP values reveals a remarkable low substituent parameter of χ = –18.5 cm–1 for the NP(tmg)3 group. In addition, we prepared the corresponding gold(I) complexes and determined their solid‐state structures using single‐crystal X‐ray diffraction studies to analyze the steric profile of the new phosphine ligands.

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Mono‐Phosphazenyl Phosphines (R₂N)₃P=N–P(NR₂)₂ – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates

Kögel

Ullrich

Kovačević

et al. 2020

Zeitschrift anorg allge chemie

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We present a convenient three‐step synthesis of amino substituted phosphazenyl phosphines of the general formula (R2N)3P=N–P(NR2)2 [NR2 = N(CH2)4, N(CH2)5, N(CH2)6]. These easily accessible mixed valent compounds display a surprisingly high proton affinity and basicity in the same range as the corresponding Schwesinger diphosphazene (Me2N)3P=N–P=NEt(NMe2)2 (Et‐P2) and Verkade's proazaphosphatrane superbases. Within the central [PIII–N=PV] scaffold, the phosphine PIII and not the phosphazene NIII atom is the center of highest proton affinity, basicity and donor strength. As P‐bases, the title compounds display calculated proton affinities between 265.8 (NR2 = NMe2) and 274.7 kcal·mol–1 [NR2 = N(CH2)4] and pKBH+ values between 26.4 (NR2 = NMe2) and 31.5 [NR2 = N(CH2)4] on the acetonitrile scale. As P‐nucleophiles, they are key intermediates in the synthesis of hyperbasic bis(diphosphazene) proton sponges, chiral bis(diphosphazene) proton pincers, bisphosphazides, and superbasic P2‐bisylides. Their Staudinger reactions as nucleophile towards 1,8‐diazidonaphthalene leading to 1,8‐naphthalene‐bisphosphazides is described in detail. The donor strength of the title compounds towards fragments [Se] and [Ni(CO)3] is in the same range as that of N‐heterocyclic carbenes.

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Synthesis and multinuclear NMR characterization of iminophosphoranyl phosphines and silanes

Cited by 5 publications

References 18 publications

Stable Carbenes

Stable Carbenes

Effective Control of the Electron‐donating Ability of Phosphines by using Phosphazenyl and Phosphoniumylidyl Substituents

Mono‐Phosphazenyl Phosphines (R₂N)₃P=N–P(NR₂)₂ – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates

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Synthesis and multinuclear NMR characterization of iminophosphoranyl phosphines and silanes

Cited by 5 publications

References 18 publications

Stable Carbenes

Stable Carbenes

Effective Control of the Electron‐donating Ability of Phosphines by using Phosphazenyl and Phosphoniumylidyl Substituents

Mono‐Phosphazenyl Phosphines (R2N)3P=N–P(NR2)2 – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates

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Mono‐Phosphazenyl Phosphines (R₂N)₃P=N–P(NR₂)₂ – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates