Reactions of Co2(CO)6(RC≡CR′) (RC 2R′-hydroxy- or alkoxysilyl-alkynes) with tetraethyl- orthosilicate

Journal of Sol-Gel Science and Technology

Volumn 38, Issue 3, 2006, Pages 283-292

  Arrais, Aldo ^a   Boccaleri, Enrico ^b   Sappa, Enrico ^b   Secco, Andrea ^b  

^a UNIVERSITY OF TURIN   (Italy)

^b UNIVERSITY OF EASTERN PIEDMONT   (Italy)

Author keywords

Alkyne diols; Cobalt carbonyls; Inorganic organometallic sol gel materials; Triethoxysilyl alkynes

Indexed keywords

MASS SPECTROMETRY; REACTION KINETICS; SCANNING ELECTRON MICROSCOPY; SILICATES; SOL-GELS; SYNTHESIS (CHEMICAL); X RAY DIFFRACTION;

ALKYNE DIOLS; COBALT CARBONYLS; INORGANIC ORGANOMETALLIC SOL GEL MATERIALS; TRIETHOXYSILYL ALKYNES;

COBALT COMPOUNDS;

EID: 33744740429     PISSN: 09280707     EISSN: None     Source Type: Journal    
DOI: 10.1007/s10971-006-6782-7     Document Type: Article

References (38)

1. See for example: Corriu RJP, Leclerq D (1996) Angew Chem Int Ed 35:1420-1436;
2. (b) Schubert U (1996) J Chem Soc Dalton Trans 3343-3348
3. See for example: (a) Castiglioni M, Deabate S, Garrone E, Giordano R, Onida B, Predieri G, Sappa E (1997) J Cluster Sci 8:381-405;
4. (b) Bonelli B, Brait S, Garrone E, Giordano R, Sappa E, Verre F (2000) J Cluster Sci 11:307-326
5. An account of the history of surface organometallic chemistry is in: Roberto D, Psaro R, Ugo R (1993) Organometallics 12:2292-2296
6. (a) Deabate S, King PJ, Sappa E (1999) In: Braunstein P, Oro LA, Raithby PR (eds) Metal clusters in chemistry, vol. 2, Ch. 8 Wiley-VCH, Weinheim, p. 796;
7. (b) Charmant JPH, King PJ, Quesada-Pato R, Sappa E, Shaefer C (2001) J Chem Soc Dalton Trans 46-51;
8. (c) King PJ, Sappa E, Sciacca C (2002) Inorg Chim Acta 334:131-141
9. See for example: Predieri G, Tiripicchio A, Tiripicchio Camellini M, Costa M, Sappa E (1992) J Organomet Chem 423:129-139
10. (a) Gervasio G, Marabello D, King PJ, Sappa E, Secco A (2003) J Organomet Chem 671:137-144;
11. (b) Gervasio G, Marabello D, Sappa E, Secco A (2004) J Organomet Chem 689:35-42
12. See for example: (a) Heck RF (1968) In: Wender I, Pino P (eds) Organic syntheses via metal carbonyls, vol. I, Wiley-Interscience, New York, p. 373;
13. (b) Kemmitt ROW, Russel D (1982) In: Wilkinson G, Stone FGA, Abel EW (eds) Comprehensive organometallic chemistry, vol. 5, Pergamon, Oxford, p. 1;
14. (c) Varadi G, Marko L (1968) In: Bemal I (ed), Stereochemistry of organometallic and inorganic compounds, vol. 1, Elsevier, Amsterdam, p. 358
15. See for example: (a) Nicholas KM (1987) Ace Chem Res 20:207-214;
16. (b) Me Glinchey MJ, Girard L, Ruffolo R (1985) Coord Chem Rev 143:331-381;
17. (c) Bradley DH, Khan MA, Nicholas KM (1989) Organometallics 8:554-556;
18. Bradley DH, Khan MA, Nicholas KM (1992) Organometallics 11:2598-2607;
19. (d) Amouri H, Da Silva C, Malezieux B, Andres R, Vaissermann J, Gruselle M (2000) Inorg Chem 39:5053-5058;
20. (e) Gruselle M, Malezieux B, Vaissermann J, Amouri H. (1998) Organometallics 17:2337-2343
21. (a) Choualeb A, Rosé J, Braunstein P, Welter R (2003) Organometallics 22:2688-2693;
22. (b) Choualeb A, Braunstein P, Rosé J, Bouaoud S-E, Welter R (2003) Organometallics 22:4405-4417;
23. (c) Choualeb A, Braunstein P, Rosé J, Welter R (2004) Inorg Chem 43: 57-71
24. Complex I does not react with methanol or ethanol unless in the presence of catalysts (e.g. HC1). It was therefore possible - in some instances- to use the alcohols for improving the solubility of BUD which is only slightly soluble in heptane. In several reactions, however, complexes contaning MeO or EtO groups were obtained besides other products
25. 2 adduct. We found two different signals for the OH which are not easily explainable if not hypothesizing that, in the NMR solvents, the complex gives a 1/1 adduct
26. 3 (ca 20 mmol) of Propargyl Alcohol; the suspension was refluxed for l min, after which time the colour turned to deep red, deposition of large amounts of a brown material (insoluble in hydrocarbons, methanol and water and sparingly soluble in acetone) and development of gas was observed. After filtering, t.l.c. purification of the red solution gave one red band (complex 2a, 45% ca) and decomposition
27. 3]
28. 3 of HCl (37%) and warmed at 60°C for 40 min. After cooling light brown solid materials were formed. These have been the subject of IR, UV-NIR, TGA, XRD and NMR analyses, but, until now, a univoque evidence for their nature has not been obtained. In our opinion these materials are hydroor alcohol-gels containing polymerised BUD and oxygen-based chromophores. Interestingly, the formation of hydrogels and alcohol-gels presumably occurs also during the formation of the silica containing sol-gel materials and is probably a process competitive with the hydrolysis of TEOS.(b). In the Reppe technology, reactions of BUD and propargyl alcohol led to THF, lactones and other oxygen-containing products. See for example: R.J. Tedeschi, Acetylene-based chemicals from coal and other natural resources (M.Dekker, New York, 1982)
29. 29Si NMR a signal at -45.83 is observed
30. See for example: (a) Kondratenko K, El Hafa H, Gruselle M, Vaissermann J, Jaouen G, McGlinchey MJ (1995) J Am Chem Soc 117:6907-6913;
31. (b) Osella D, Ravera M, Nervi C, Cavigiolio G, Vincenti M, Vessieres A, Jaouen G (2000) Eur J Inorg Chem 491-497
32. (a) Lang H, Lay U (1990) J Organomet Chem 388:C1-C4;
33. (b) Lang H, Lay U, Weinmann M (1992) J Organomet Chem 436:265-267;
34. Corriu RJP, Moreau JJE, Praet H (1989) J Organomet Chem 376:C39-C43
35. Golovko VG, Mays MJ, Woods AD (2002) New J Chem 26:1706-1708
36. Soleilhavoup M, Saccavini C, Lepetit C, Lavigne G, Maurette L, Donnadieu B, Chauvin R (2002) Organometallics 21:871-883
37. Cavagnino M, Sappa E, Secco A, unpublished results
38. It has been recently reported that alkynes (among other organic molecules) can be used to form functional monolayers bound through Si-C bonds. Buriak JM (1999) J Chem Soc Chem Commun 1051-1060