Bis(difenilofosfino)metan

1,1-Bis(difenilfosfino)metan (dppm), CH ₂ (PPh ₂) ₂ formulasiga ega bo'lgan fosfororganik birikma. Dppm, oq, kristall kukun, ligand sifatida noorganik va organometall kimyoda qo'llaniladi.^[1] Bu aniqroq xelatlovchi liganddir, chunki u ikkita fosfor donor atomlari bilan metallar bilan bog'lana oladigan liganddir. Tabiiy tishlash burchagi 73 °.^[2]

Sintez va reaktivlik[tahrir | manbasini tahrirlash]

1,1-Bis(difenilfosfino)metan birinchi marta natriy difenilfosfid (Ph₂PNa) ning diklorometan bilan reaksiyasi natijasida olingan:^[3]

Ph ₃ P + 2 Na → Ph ₂ PNa + NaPh

2NaPPh ₂ + CH ₂ Cl ₂ → Ph ₂ PCH ₂ PPh ₂ + 2 NaCl

Dppm (va ayniqsa uning komplekslari) tarkibidagi metilen guruhi (CH ₂) engil kislotali. Ligand oksidlanib, tegishli oksidlar va sulfidlar CH ₂ [P(E)Ph ₂ ] ₂ (E = O, S) hosil bo'lishi mumkin. Metilen guruhi bu hosilalarda yanada kislotali bo'ladi.

Koordinatsion kimyo[tahrir | manbasini tahrirlash]

Xelatlovchi ligand sifatida 1,1-bis(difenilfosfino)metan MP₂C tarkibiy qismlari bilan toʻrt aʼzoli halqa hosil qiladi. Ligand besh a'zoli M₂P₂C halqalarini o'z ichiga olgan bimetalik komplekslarning shakllanishiga yordam beradi. Shu tarzda, dppm bimetalik komplekslarning shakllanishiga yordam beradi. Bunday misollardan biri dipalladiy xlorid, Pd₂Cl₂(dppm)₂. Ushbu kompleksda Pd markazlari uchun oksidlanish darajasi I. Bis(difenilfosfino)metan A-ramka komplekslari deb nomlanuvchi koordinatsion birikmalar oilasini keltirib chiqaradi.^[4]

[Pd ₂ Cl ₂ (dppm) ₂ ] ning to'p va tayoq modeli.^[5]

Manbalar[tahrir | manbasini tahrirlash]

orga

↑ Humphrey, Mark G.; Lee, Jeanne; Hockless, David C.R.; Skelton, Brian W.; White, Allan H. (1993). „Mixed-Metal Cluster Chemistry“. Organometallics. 12-jild, № 3468. 3468-bet. doi:10.1021/om00033a017.
↑ Birkholz, Mandy-Nicole; Freixa, Zoraida; van Leeuwen, Piet W. N. M. (2009). „Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions“. Chemical Society Reviews. 38-jild, № 4. 1099-bet. doi:10.1039/B806211K. PMID 19421583.
↑ W. Hewertson; H. R. Watson (1962). „The preparation of di- and tri-tertiary phosphines“. J. Chem. Soc. 12-jild. 1490–1494-bet. doi:10.1039/JR9620001490.
↑ Albéniz, Ana C.; Espinet, Pablo (2006). "Encyclopedia of Inorganic Chemistry". Encyclopedia of Inorganic Chemistry. doi:10.1002/0470862106.ia178. ISBN 0-470-86078-2.
↑ G. Besenyei; L. Párkányia; E. Gács-Baitza; B. R. James (January 2002). „Crystallographic characterization of the palladium(I) dimers, syn-Pd2Cl2(dppmMe)2 and Pd2Cl2(dppm)2; solution conformational behavior of syn- and anti-Pd2Cl2(dppmMe)2 and their (μ-Se) adducts [dppmMe=μ-1,1-bis(diphenylphosphino)ethane, and DPPM=μ-bis(diphenylphosphino)methane]“. Inorg. Chim. Acta. 327-jild, № 1. 179–187-bet. doi:10.1016/S0020-1693(01)00682-X.

[1] Humphrey, Mark G.; Lee, Jeanne; Hockless, David C.R.; Skelton, Brian W.; White, Allan H. (1993). „Mixed-Metal Cluster Chemistry“. Organometallics. 12-jild, № 3468. 3468-bet. doi:10.1021/om00033a017.

[vanLeeuwen-2] Birkholz, Mandy-Nicole; Freixa, Zoraida; van Leeuwen, Piet W. N. M. (2009). „Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions“. Chemical Society Reviews. 38-jild, № 4. 1099-bet. doi:10.1039/B806211K. PMID 19421583.

[3] W. Hewertson; H. R. Watson (1962). „The preparation of di- and tri-tertiary phosphines“. J. Chem. Soc. 12-jild. 1490–1494-bet. doi:10.1039/JR9620001490.

[4] Albéniz, Ana C.; Espinet, Pablo (2006). "Encyclopedia of Inorganic Chemistry". Encyclopedia of Inorganic Chemistry. doi:10.1002/0470862106.ia178. ISBN 0-470-86078-2.

[5] G. Besenyei; L. Párkányia; E. Gács-Baitza; B. R. James (January 2002). „Crystallographic characterization of the palladium(I) dimers, syn-Pd2Cl2(dppmMe)2 and Pd2Cl2(dppm)2; solution conformational behavior of syn- and anti-Pd2Cl2(dppmMe)2 and their (μ-Se) adducts [dppmMe=μ-1,1-bis(diphenylphosphino)ethane, and DPPM=μ-bis(diphenylphosphino)methane]“. Inorg. Chim. Acta. 327-jild, № 1. 179–187-bet. doi:10.1016/S0020-1693(01)00682-X.

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