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Pregled bibliografske jedinice broj: 1088848

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


Kögel, Julius F.; Ullrich, Sebastian; Kovačević, Borislav; Wagner, Sebastian; Sundermeyer, Jörg
Mono‐Phosphazenyl Phosphines (R 2 N) 3 P=N–P(NR 2 ) 2 – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates // Zeitschrift für anorganische und allgemeine Chemie, 646 (2020), 13; 923-932 doi:10.1002/zaac.202000108 (međunarodna recenzija, članak, znanstveni)


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

Autori
Kögel, Julius F. ; Ullrich, Sebastian ; Kovačević, Borislav ; Wagner, Sebastian ; Sundermeyer, Jörg

Izvornik
Zeitschrift für anorganische und allgemeine Chemie (0044-2313) 646 (2020), 13; 923-932

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Basicity ; Phosphines ; Phosphazenes ; Density functional calculations ; Tolman electronic parameter

Sažetak
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.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Ustanove:
Institut "Ruđer Bošković", Zagreb

Profili:

Avatar Url Borislav Kovačević (autor)

Citiraj ovu publikaciju

Kögel, Julius F.; Ullrich, Sebastian; Kovačević, Borislav; Wagner, Sebastian; Sundermeyer, Jörg
Mono‐Phosphazenyl Phosphines (R 2 N) 3 P=N–P(NR 2 ) 2 – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates // Zeitschrift für anorganische und allgemeine Chemie, 646 (2020), 13; 923-932 doi:10.1002/zaac.202000108 (međunarodna recenzija, članak, znanstveni)
Kögel, J., Ullrich, S., Kovačević, B., Wagner, S. & Sundermeyer, J. (2020) Mono‐Phosphazenyl Phosphines (R 2 N) 3 P=N–P(NR 2 ) 2 – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates. Zeitschrift für anorganische und allgemeine Chemie, 646 (13), 923-932 doi:10.1002/zaac.202000108.
@article{article, year = {2020}, pages = {923-932}, DOI = {10.1002/zaac.202000108}, keywords = {Basicity, Phosphines, Phosphazenes, Density functional calculations, Tolman electronic parameter}, journal = {Zeitschrift f\"{u}r anorganische und allgemeine Chemie}, doi = {10.1002/zaac.202000108}, volume = {646}, number = {13}, issn = {0044-2313}, title = {Mono‐Phosphazenyl Phosphines (R 2 N) 3 P=N–P(NR 2 ) 2 – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates}, keyword = {Basicity, Phosphines, Phosphazenes, Density functional calculations, Tolman electronic parameter} }
@article{article, year = {2020}, pages = {923-932}, DOI = {10.1002/zaac.202000108}, keywords = {Basicity, Phosphines, Phosphazenes, Density functional calculations, Tolman electronic parameter}, journal = {Zeitschrift f\"{u}r anorganische und allgemeine Chemie}, doi = {10.1002/zaac.202000108}, volume = {646}, number = {13}, issn = {0044-2313}, title = {Mono‐Phosphazenyl Phosphines (R 2 N) 3 P=N–P(NR 2 ) 2 – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates}, keyword = {Basicity, Phosphines, Phosphazenes, Density functional calculations, Tolman electronic parameter} }

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus


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