مركب معدن-فورمالديهايد

المركب المعدني - الفورمالديهايدي (بالإنجليزية: metal-formaldehyde complex)‏ هو معقد تناسقي يضم ربِيطة الفورمالديهايد مع رابطتين مع ذرات المعدن (η 2 -CH 2 O). أُبلغ عن تواجد هذا النوع من الرَّبِيطة في كل من المجمعات أحادية المعدن وثنائية المعدن.

التاريخ

أُعلن عن روابط الفورمالديهايد المعدنية للتنغستن (W)، والأوزميوم (Os)،[1] والفاناديوم (V)،[2] والرينيوم (Re)،[3] والزركونيوم (Zr)،[4][5][6] والروثينيوم (Ru)،[7] والنيوبيوم (Nb).[8]

في عام 1984، أعلن جرين وزملاؤه عن المادة الصلبة البلورية الصفراء W(PMe 3 ) 4 (η 2 -CH 2 O)H 2 . كان ذلك نتيجة إضافة الميثانول إلى W(PMe3)4(η2-CH2PMe2)H

يمكن هدرجة W(PMe3)4(η2-CH2O)H2 لإعطاء W(PMe3)4(MeO)H3، ثم هدرجتها مرة أخرى لإعادة تشكيل الميثانول وتوليد W(PMe3)4H4.[9] في عام 1986، أظهر جرين وباركين المزيد من التفاعلات لـ W(PMe 3 ) 4 (η 2 -CH 2 O)H 2 . عند إضافة CO أو CO 2 ، ينتج W(PMe 3 ) 4 (η 2 -CH 2 O)H 2 fac -W(PMe 3 ) 3 (CO) 3 وW(PMe 3 ) 4 (κ 2 -O 2 CO)H 2 ، على التوالي، تمامًا مثل سابقه.

يتفاعل W(PMe 3 ) 4 (η 2 -CH 2 O)H 2 أيضًا مع البيوتا-1،3-ديين ليعطي W(PMe 3 ) 3 (η 2 -CH 2 O)(η-C 4 H 6 ). [10]

يمكن أيضًا استخدام W(PMe 3 ) 4 (η 2 -CH 2 O)H 2 كطريق لمزيد من دورات الأكسوميتالاسيك عن طريق إضافة الإيثيلين والتبريد السريع إلى -80 درجة مئوية. تتكون البلورات الخضراء الناتجة من W(OCH 2 CH 2 CH 2 )(PMe 3 ) 2 (η 2 -C 2 H 4 ) 2 ، مع وجود كل من ربيطة الإيثيلين على المستوى الاستوائي أو ربيطة الإيثيلين cis - للأكسجين الرابط في الاتجاه المحوري. يؤدي التفاعل الإضافي مع الإيثيلين إلى إنتاج عبر -W(PMe 3 ) 4 (η 2 -C 2 H 4 ) 2 وW(PMe 3 ) 4 (CO)H 2 . [11]

التفاعلات المبلغ عنها لـ W(PMe 3 ) 4 (η 2 -CH 2 O)H 2 .

المراجع

  1. ^ Clark، G.R.؛ Headford، C.E.L.؛ Marsden، K.؛ Roper، W.R. (يونيو 1982). "Synthesis, structure and reactions of a dihapto-formaldehyde complex, Os(η2-CH2O)(CO)2(PPh3)2". Journal of Organometallic Chemistry. ج. 231 ع. 4: 335–360. DOI:10.1016/s0022-328x(00)81212-7. ISSN:0022-328X.
  2. ^ Gambarotta, S.; Floriani, C.; Chiesi-Villa, A.; Guastini, C. (Apr 1982). "Metal-formaldehyde chemistry: coordination, disproportionation and Lewis acid-promoted transformation to oxymethylene derivatives". Journal of the American Chemical Society (بالإنجليزية). 104 (7): 2019–2020. DOI:10.1021/ja00371a038. ISSN:0002-7863. Archived from the original on 2024-03-17.
  3. ^ Buhro, William E.; Patton, Alan T.; Strouse, Charles E.; Gladysz, J. A.; McCormick, Fred B.; Etter, Margaret C. (Feb 1983). "Syntheses, chemical properties, and x-ray crystal structures of rhenium formaldehyde and thioformaldehyde complexes". Journal of the American Chemical Society (بالإنجليزية). 105 (4): 1056–1058. DOI:10.1021/ja00342a070. ISSN:0002-7863. Archived from the original on 2024-03-17.
  4. ^ Gambarotta, S.; Floriani, C.; Chiesi-Villa, A.; Guastini, C. (Mar 1983). "Genesis, bonding mode and reaction with carbon monoxide of an oxymethylene unit bridging two metal atoms". Journal of the American Chemical Society (بالإنجليزية). 105 (6): 1690–1691. DOI:10.1021/ja00344a066. ISSN:0002-7863. Archived from the original on 2024-03-17.
  5. ^ Kropp, Kurt; Skibbe, Volker; Erker, Gerhard; Krueger, Carl (May 1983). "Fischer-Tropsch intermediates: tris[(.eta.2-formaldehyde)zirconocene] from the carbonylation of a zirconium hydride". Journal of the American Chemical Society (بالإنجليزية). 105 (10): 3353–3354. DOI:10.1021/ja00348a075. ISSN:0002-7863. Archived from the original on 2024-03-17.
  6. ^ Fachinetti, Giuseppe; Floriani, Carlo; Pucci, Sergio (1 Jan 1978). "Stoicheiometric reduction of CO and CO2 to methanol: evidence for carbon monoxide insertion into zirconium–hydrogen bond". Journal of the Chemical Society, Chemical Communications (بالإنجليزية) (6): 269–270. DOI:10.1039/C39780000269. ISSN:0022-4936. Archived from the original on 2024-06-04.
  7. ^ Chaudret, Bruno N.; Cole-Hamilton, David J.; Nohr, Ronald S.; Wilkinson, Geoffrey (1 Jan 1977). "The reactions of chlorohydrido- and dichloro-tris(triphenylphosphine)ruthenium(II) with alkali hydroxides and alkoxides. Hydridohydroxobis(triphenylphosphine)ruthenium(II) monosolvates, their reactions and related compounds". Journal of the Chemical Society, Dalton Transactions (بالإنجليزية) (16): 1546–1557. DOI:10.1039/DT9770001546. ISSN:1364-5447. Archived from the original on 2024-04-15.
  8. ^ Wolczanski, Peter T.; Threlkel, Richard S.; Bercaw, John E. (Jan 1979). "Reduction of coordinated carbon monoxide to "zirconoxy" carbenes with permethylzirconocene dihydride". Journal of the American Chemical Society (بالإنجليزية). 101 (1): 218–220. DOI:10.1021/ja00495a037. ISSN:0002-7863. Archived from the original on 2024-03-17.
  9. ^ Green, Malcolm L. H.; Parkin, Gerard; Moynihan, Kelly J.; Prout, Keith (1 Jan 1984). "Formation of an η2-formaldehyde compound from methanol and its hydrogenation giving methanol". Journal of the Chemical Society, Chemical Communications (بالإنجليزية) (22): 1540. DOI:10.1039/C39840001540. ISSN:0022-4936. Archived from the original on 2024-02-19.
  10. ^ Green, Malcolm L. H.; Parkin, Gerard (1 Jan 1986). "Ethylene insertion into the W–C bond of the η2-formaldehyde ligand system of W(PMe3)4(η2-CH2O)H2 giving the oxometallacyclopentane derivative W(OCH2CH2CH2)(PMe3)2(C2H4)2 and related studies". Journal of the Chemical Society, Chemical Communications (بالإنجليزية) (1): 90–91. DOI:10.1039/C39860000090. ISSN:0022-4936. Archived from the original on 2024-02-22.
  11. ^ Green, Malcolm L. H.; Parkin, Gerard (1 Jan 1986). "Ethylene insertion into the W–C bond of the η2-formaldehyde ligand system of W(PMe3)4(η2-CH2O)H2 giving the oxometallacyclopentane derivative W(OCH2CH2CH2)(PMe3)2(C2H4)2 and related studies". Journal of the Chemical Society, Chemical Communications (بالإنجليزية) (1): 90–91. DOI:10.1039/C39860000090. ISSN:0022-4936. Archived from the original on 2024-02-22.
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