Organarodiy kimyosi

Organarodiy kimyo - rodyum - uglerod kimyoviy bog'lanishini o'z ichiga olgan organometalik birikmalar kimyosi va organik reaksiyalarda katalizator sifatida rodyum va rodyum birikmalarini o'rganish.^[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[tahrir | manbasini tahrirlash]

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

Rodiy (0) komplekslari ikkilik karbonillar bo'lib, 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 o'laroq, Rh ₂ (CO) ₈ juda labildir.

Rodiy(I)[tahrir | manbasini tahrirlash]

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 bo'lmasa ham, Uilkinson katalizatori (RhCl(PPh 3) 3)), muhim katalizatorlar ro'yxatiga kiritilgan. Oddiy olefin komplekslari xlorobis (etilen) rodiy dimer, xlorobis (siklookten) rodiy dimer va siklooktadien rodiy xlorid dimerlari ko'pincha "RhCl" manbalari sifatida ishlatiladi, bu esa alken ligandlarining labilligi yoki ularning vodorodga qayta ta'sirchanligidan foydalanadi. (ē 5 - Cp)RhL 2 Rh 2 Cl 2 L 4 (L = CO, C 2 H 4) dan olingan.

Rodiy (II)[tahrir | manbasini tahrirlash]

Kobalt (II) komplekslarining tarqalishidan farqli o'laroq, rodyum (II) birikmalari kam uchraydi. Rodosen sendvich birikmasi bunga misoldir, hatto u dimerik Rh(I) hosilasi bilan muvozanatda ham mavjud. Organometalik bo'lmasa-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)[tahrir | manbasini tahrirlash]

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

Rodiy(V)[tahrir | manbasini tahrirlash]

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

Metall sikllar[tahrir | manbasini tahrirlash]

Siklometallangan rodyum birikmalari metallorganik kimyoning muhim sinfini tashkil qiladi. Bunday birikmalar adabiyotda yaxshi hujjatlashtirilgan bo'lsa-da, azo funksiyasi bilan rodiy (III) siklometalatlar zaxiradir. Ushbu toifaga odatiy misol, ya'ni. 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 bo'lish mexanizmi azo-azotni dastlabki muvofiqlashtirish, so'ngra kulon fenil halqasida elektrofil almashtirish orqali davom etishi tasvirlangan. PPh ₃ C(sp ³)-S parchalanish jarayonida hal qiluvchi rol o'ynaydi. Yagona elektron uzatish (SET) mexanizmi orqali reduktiv bo'linish, ehtimol, C-S bog'lanishining ajralishi uchun ishlaydi. O'xshash (fenylazo)fenolato birikmasidan farqli o'laroq, ortometallangan tiolato kompleksi Ag/AgCl ga nisbatan 0,82 V da to'liq qaytariladigan oksidlanish to'lqinini namoyish etadi va bu javob asosan tiolato oltingugurt atomida joylashgan bo'lishi kerak.^[4]

Asosiy ilovalar[tahrir | manbasini tahrirlash]

Yuqori narxga qaramay, rodyum tijoriy katalizator sifatida juda ko'p ishoniladi.

Sirka kislota va sirka angidrid sintezi[tahrir | manbasini tahrirlash]

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

Sirka kislotasini ishlab chiqarish uchun Monsanto jarayonining katalitik aylanishi.

Katalitik faol tur anion cis -[Rh(CO) ₂ I ₂ ] ^-.^[5] metilyodid bilan oksidlovchi qo'shilishdan o'tadi. 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[tahrir | manbasini tahrirlash]

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

Gidroformilatsiyalar ko'pincha 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}}}}

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

{\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}}}}

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

{\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}}}}

</mtext></mover></mrow><mo>

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

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

{\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}}}}

</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}}}}

</mo><mtext>

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

</mtext><mo stretchy="false">

{\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}}}}

</mn></mrow></msubsup><mo stretchy="false">

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

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

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

</mn></mrow></msubsup></mrow></mpadded></munderover></mrow><mrow class="MJX-TeXAtom-ORD"><mover><mrow><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}}}}

</mn></mrow></msubsup><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}}}}

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

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

</mtext></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}}}}

</img>

Gidrogenatsiya[tahrir | manbasini tahrirlash]

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

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

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

Nitrobenzolning qaytarilishi bu birikma turi bilan katalizlangan yana bir reaksiya:

Manbalar[tahrir | manbasini tahrirlash]

↑ 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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