Organarodiy kimyosi

Organarodiy kimyo – rodyum – uglerod kimyoviy bogʻlanishini oʻz ichiga olgan organometalik birikmalar kimyosi va organik reaksiyalarda katalizator sifatida rodyum va rodyum birikmalarini oʻrganish.^[1]

Barqaror organarodiy birikmalari va vaqtinchalik organarodiy oraliq moddalari olefin gidroformilatsiyasi, olefin gidrogenatsiyasi, olefin izomerizatsiyasi va Monsanto jarayoni kabi katalizator sifatida ishlatiladi^[2]

Asosiy oksidlanish darajalari asosida tasniflash

Organometalik rodiy birikmalari iridiy bilan bir qatorda koʻp xususiyatlarga ega, ammo kobalt bilan kamroq. Rodiy -III dan +V gacha oksidlanish darajasida boʻlishi mumkin, ammo rodiy (I) va rodiy (III) koʻproq tarqalgan. Rodyum (I) birikmalari (d ⁸ konfiguratsiyasi) odatda kvadrat tekislik yoki trigonal bipiramidal geometriyalarda paydo boʻladi, rodyum (III) birikmalari (d ⁶ konfiguratsiya) odatda oktaedral geometriyaga ega.^[2]

Rodiy (0) komplekslari ikkilik karbonillar boʻlib, asosiy misollar tetrarhodium dodecacarbonyl, Rh ₄ (CO) ₁₀ va hexadecacarbonylhexarhodium, Rh ₆ (CO) ₁₆. Bu birikmalar rodiy (III) tuzlari yoki Rh ₂ Cl ₂ (CO) ₄ ning qaytaruvchi karbonillanishi natijasida olinadi. Gomologik Co ₂ (CO) ₈ ning barqarorligidan farqli oʻlaroq, Rh ₂ (CO) ₈ juda labildir.

Rodiy(I)

Rodiy (I) komplekslari muhim bir hil katalizatorlardir. Umumiy komplekslarga bis(trifenilfosfin)rodiy karbonilxlorid, xlorobis(etilen)rodiy dimer, siklooktadien rodiy xlorid dimer, xlorobis(siklookten)rodiy dimer, dikarbonil(atsetilxlorid) va karbonil (todilaxlorid) kiradi. Rasmiy organometalik boʻlmasa ham, Uilkinson katalizatori (RhCl(PPh 3) 3)), muhim katalizatorlar roʻyxatiga kiritilgan. Oddiy olefin komplekslari xlorobis (etilen) rodiy dimer, xlorobis (siklookten) rodiy dimer va siklooktadien rodiy xlorid dimerlari koʻpincha „RhCl“ manbalari sifatida ishlatiladi, bu esa alken ligandlarining labilligi yoki ularning vodorodga qayta taʼsirchanligidan foydalanadi. (ē 5 – Cp)RhL 2 Rh 2 Cl 2 L 4 (L = CO, C 2 H 4) dan olingan.

Rodiy (II)

Kobalt (II) komplekslarining tarqalishidan farqli oʻlaroq, rodyum (II) birikmalari kam uchraydi. Rodosen sendvich birikmasi bunga misoldir, hatto u dimerik Rh(I) hosilasi bilan muvozanatda ham mavjud. Organometalik boʻlmasa-da, rodyum (II) asetat (Rh ₂ (OAc) ₄) organometalik oraliq mahsulotlar orqali siklopropanatsiyalarni katalizlaydi. Rodiy (II) porfirin komplekslari metan bilan reaksiyaga kirishadi.^[3]

Rodiy (III)

Rodiy odatda Rh (III) oksidlanish holatida tijorat sifatida etkazib beriladi, asosiy boshlangʻich reagent gidratlangan rodyum trikloriddir. Ikkinchisi olefinlar va CO bilan reaksiyaga kirishib, organometalik komplekslarni beradi, koʻpincha Rh (I) ning pasayishi bilan birga keladi. Rodiyning siklopentadienil komplekslari yarim sendvich birikma pentametilsiklopentadienil rodyum dixlorid dimerini oʻz ichiga oladi.

Rodiy(V)

Rh (V) ni barqarorlashtirish uchun kuchli donor ligandlar – gidrid, silil, boril kerak. Bu oksidlanish darajasi borillanish reaksiyalarida chaqiriladi.

Rh-katalizlangan borillanish reaksiyalari Rh (V) oraliq moddalarni oʻz ichiga oladi.

Metall sikllar

Siklometallangan rodyum birikmalari metallorganik kimyoning muhim sinfini tashkil qiladi. Bunday birikmalar adabiyotda yaxshi hujjatlashtirilgan boʻlsa-da, azo funksiyasi bilan rodiy (III) siklometalatlar zaxiradir. Ushbu toifaga odatiy misol, yaʼni. yangi heksakoordinatsiyalangan ortometallangan rodiy (III) tiolato kompleksi trans-[Rh(C ^∧ N ^∧ S)Cl(PPh ₃) ₂ ] tarkibida benzil 2-(fenilzo)fenil tioeter va RhCl ₃ ·3H ₂ O ning ortiqcha mavjudligidan sintez qilindi. PPh ₃ in situ C(sp ²)−H va C(sp ³)−S bogʻlanish qirqishlari orqali. Bu (fenylazo)tiolat ligandining koordinatsion birikmasiga birinchi misol. Ortometallangan azobenzol hosilasining hosil boʻlish mexanizmi azo-azotni dastlabki muvofiqlashtirish, soʻngra kulon fenil halqasida elektrofil almashtirish orqali davom etishi tasvirlangan. PPh ₃ C(sp ³)-S parchalanish jarayonida hal qiluvchi rol oʻynaydi. Yagona elektron uzatish (SET) mexanizmi orqali reduktiv boʻlinish, ehtimol, C-S bogʻlanishining ajralishi uchun ishlaydi. Oʻxshash (fenylazo)fenolato birikmasidan farqli oʻlaroq, ortometallangan tiolato kompleksi Ag/AgCl ga nisbatan 0,82 V da toʻliq qaytariladigan oksidlanish toʻlqinini namoyish etadi va bu javob asosan tiolato oltingugurt atomida joylashgan boʻlishi kerak.^[4]

Asosiy ilovalar

Yuqori narxga qaramay, rodyum tijoriy katalizator sifatida juda koʻp ishoniladi.

Sirka kislota va sirka angidrid sintezi

Monsanto jarayoni metanolning katalitik karbonillanishi orqali sirka kislotasini ishlab chiqarishning sanoat usulidir, garchi u asosan iridiyga asoslangan Cativa jarayoni bilan almashtirilgan boʻlsa ham.

Sirka kislotasini ishlab chiqarish uchun Monsanto jarayonining katalitik aylanishi.

Katalitik faol tur anion cis -[Rh(CO) ₂ I ₂ ] ^-.^[5] metilyodid bilan oksidlovchi qoʻshilishdan oʻtadi. Tegishli Tennessee Eastman sirka angidrid jarayoni metil asetatning karbonillanishi orqali sirka angidridini beradi.^[6]

CH ₃ CO ₂ CH ₃ + CO → (CH ₃ CO) ₂ O

Gidroformillanish

Rodiy asosidagi gidroformillanish katalizatori, bu yerda PAr ₃ = trifenilfosfin yoki uning sulfonlangan analogi Tppts.

Gidroformilatsiyalar koʻpincha rodiy asosidagi katalizatorlarga tayanadi. Suvda eruvchan katalizatorlar ham ishlab chiqilgan. Ular mahsulotlarni katalizatordan ajratishni osonlashtiradi.^[7]

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</mo></mrow><msubsup><mtext>

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</mn></mrow></msubsup></mrow><mtext>

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</mtext></mrow><mo>

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</mo><mtext>

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</mo><msubsup><mtext>

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</mtext><mrow class="MJX-TeXAtom-ORD"><mn>

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</mn></mrow></msubsup><msubsup><mtext>

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</mn></mrow></msubsup><mtext>

{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

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{\ce {{\overset {alkene}{RHC=CH2}}+{CO}+H2->[{\ce {HRh(CO)(PPh3)3}}][{\text{hydroformylation}}]{\overset {aldehydes}{RCH2CH2CHO}}}}

</img>

Gidrogenatsiya

Uilkinson katalizatori olefinlarni gidrogenlashda bir hil katalizator sifatida ishlatiladi.^[8] Kataliz mexanizmi H ₂ ning oksidlovchi qoʻshilishi, alkenning p-kompleksatsiyasi, migratsiyali kiritish (molekulyar gidridni oʻtkazish yoki olefinni kiritish) va reduktiv eliminatsiyani oʻz ichiga oladi.

Kationik organorhodium (I) katalizatorlari assimetrik gidrogenatsiyalar uchun foydalidir, ular farmatsevtika vositalari va agrokimyoviy moddalar kabi bioaktiv mahsulotlarga qoʻllanadi.^[9]

Assimetrik gidrogenlanish uchun prekatalizator [Rh(DIPAMP)(cod)] ⁺ ning tuzilishi.^[10]

Nitrobenzolning qaytarilishi bu birikma turi bilan katalizlangan yana bir reaksiya:

Manbalar

↑ Synthesis of Organometallic Compounds: A Practical Guide Sanshiro Komiya Ed. S. Komiya, M. Hurano 1997
↑ ^2,0 ^2,1 Crabtree, Robert H.. The Organometallic Chemistry of the Transition Metals, 4th, USA: Wiley-Interscience, 2005. ISBN 0-471-66256-9. Manba xatosi: Invalid <ref> tag; name "Crabtree" defined multiple times with different content
↑ Bradford B. Wayland, Sujuan Ba, Alan E. Sherry (1991). „Activation of Methane and Toluene by Rhodium(II) Porphyrin Complexes“. J. Am. Chem. Soc. 113-jild. 5305–5311-bet. doi:10.1021/ja00014a025.{{cite magazine}}: CS1 maint: multiple names: authors list ()
↑ K. Pramanik; U. Das; B. Adhikari; D. Chopra; H. Stoeckli-Evans (2008). „RhCl₃-Assisted C-H and C-S Bond Scissions: Isomeric Self-Association of Organorhodium(III) Thiolato Complex. Synthesis, Structure, and Electrochemistry“. Inorg. Chem. 47-jild, № 2. 429–438-bet. doi:10.1021/ic7016006. PMID 18161963.
↑ Hartwig, J. F. Organotransition Metal Chemistry, from Bonding to Catalysis; University Science Books: New York, 2010. ISBN 189138953X
↑ Zoeller, J. R.; Agreda, V. H.; Cook, S. L.; Lafferty, N. L.; Polichnowski, S. W.; Pond, D. M. (1992). „Eastman Chemical Company Acetic Anhydride Process“. Catalysis Today. 13-jild, № 1. 73–91-bet. doi:10.1016/0920-5861(92)80188-S.
↑ Cornils, B.; Herrmann, W. A. (eds.) „Aqueous-Phase Organometallic Catalysis“ VCH, Weinheim: 1998
↑ Hartwig, John F.. Organotransition metal chemistry- From bonding to Catalysis. University Science Books, 2010. ISBN 978-1-891389-53-5.
↑ Knowles, William S. (2002). „Asymmetric Hydrogenations (Nobel Lecture)“. Angewandte Chemie International Edition. 41-jild. 1998-bet. doi:10.1002/1521-3773(20020617)41:12<1998::AID-ANIE1998>3.0.CO;2-8.
↑ H.-J.Drexler, Songlin Zhang, Ailing Sun, A. Spannenberg, A. Arrieta, A. Preetz, D. Heller. „Cationic Rh-bisphosphine-diolefin complexes as precatalysts for enantioselective catalysis––what information do single crystal structures contain regarding product chirality?“. Tetrahedron: Asymmetry. 15-jild. 2139–50-bet. doi:10.1016/j.tetasy.2004.06.036.{{cite magazine}}: CS1 maint: multiple names: authors list ()

[1] Synthesis of Organometallic Compounds: A Practical Guide Sanshiro Komiya Ed. S. Komiya, M. Hurano 1997

[Crabtree-2] 2,0 ^2,1 Crabtree, Robert H.. The Organometallic Chemistry of the Transition Metals, 4th, USA: Wiley-Interscience, 2005. ISBN 0-471-66256-9. Manba xatosi: Invalid <ref> tag; name "Crabtree" defined multiple times with different content

[3] Bradford B. Wayland, Sujuan Ba, Alan E. Sherry (1991). „Activation of Methane and Toluene by Rhodium(II) Porphyrin Complexes“. J. Am. Chem. Soc. 113-jild. 5305–5311-bet. doi:10.1021/ja00014a025.{{cite magazine}}: CS1 maint: multiple names: authors list ()

[4] K. Pramanik; U. Das; B. Adhikari; D. Chopra; H. Stoeckli-Evans (2008). „RhCl₃-Assisted C-H and C-S Bond Scissions: Isomeric Self-Association of Organorhodium(III) Thiolato Complex. Synthesis, Structure, and Electrochemistry“. Inorg. Chem. 47-jild, № 2. 429–438-bet. doi:10.1021/ic7016006. PMID 18161963.

[5] Hartwig, J. F. Organotransition Metal Chemistry, from Bonding to Catalysis; University Science Books: New York, 2010. ISBN 189138953X

[6] Zoeller, J. R.; Agreda, V. H.; Cook, S. L.; Lafferty, N. L.; Polichnowski, S. W.; Pond, D. M. (1992). „Eastman Chemical Company Acetic Anhydride Process“. Catalysis Today. 13-jild, № 1. 73–91-bet. doi:10.1016/0920-5861(92)80188-S.

[7] Cornils, B.; Herrmann, W. A. (eds.) „Aqueous-Phase Organometallic Catalysis“ VCH, Weinheim: 1998

[8] Hartwig, John F.. Organotransition metal chemistry- From bonding to Catalysis. University Science Books, 2010. ISBN 978-1-891389-53-5.

[9] Knowles, William S. (2002). „Asymmetric Hydrogenations (Nobel Lecture)“. Angewandte Chemie International Edition. 41-jild. 1998-bet. doi:10.1002/1521-3773(20020617)41:12<1998::AID-ANIE1998>3.0.CO;2-8.

[10] H.-J.Drexler, Songlin Zhang, Ailing Sun, A. Spannenberg, A. Arrieta, A. Preetz, D. Heller. „Cationic Rh-bisphosphine-diolefin complexes as precatalysts for enantioselective catalysis––what information do single crystal structures contain regarding product chirality?“. Tetrahedron: Asymmetry. 15-jild. 2139–50-bet. doi:10.1016/j.tetasy.2004.06.036.{{cite magazine}}: CS1 maint: multiple names: authors list ()

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