Synthesis of Modified Tris(pyrazolyl)methane Ligands: Backbone Functionalization­

 

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Abstract

The deprotonation of HC(pz)₃ with n-butyllithium followed by reaction with methyl iodide, benzyl bromide and chloro­trimethylsilane produced the respective substituted ligands RC(pz)₃ [R = CH₃, C₆H₅CH₂, (CH₃)₃Si] in good yield. Analogous chemistry starting with HC(3-Phpz)₃ was only successful in high yield when the deprotonation step was carried out with LiN[Si(CH₃)₃]₂, added at low temperature, and led to the syntheses of RC(3-Phpz)₃ [R = CH₃, (CH₃)₃Si, CH₂=CHCH₂, C₆H₅CH₂]. In contrast, the alcohol derivatives HOCH₂C(pz)₃ and HOCH₂C(3-Phpz)₃ were prepared using potassium tert-butoxide for the deprotonation step followed by paraformaldehyde. For HC(3-t-Bupz)₃, deprotonation with n-butyllithium at low temperature was most successful and led to the syntheses of RC(3-t-Bupz)₃ [R = CH₃, (CH₃)₃Si, HOCH₂]. The compound HOCH₂C(pz)₃ was converted into t-BuPhCH₂OCH₂C(pz)₃ by reaction with sodium hydride and (tert-butyl)benzyl bromide. These synthetic routes have made a variety of functionalized tris(pyrazolyl)methane ligands available for studies of their coordination chemistry.

References

• 1a Trofimenko S. Prog. Inorg. Chem.  1986,  34:  141 
  Google Scholar
• 1b Shaver A. J. Organomet. Chem. Lib.  1976,  4:  157 
  Google Scholar
• 1c Trofimenko S. In Scorpionates- The Coordination Chemistry of Poly(pyrazolyl)borate Ligands   Imperial College Press; London: 1999. 
  Google Scholar
• 2a Byers PK. Canty AJ. Honeyman RT. Adv. Organomet. Chem.  1992,  34:  1 
  CrossrefGoogle Scholar
• 2b Canty AJ. Minchin NJ. Healy PC. White AH. J. Chem. Soc., Dalton Trans.  1982,  1795 
  CrossrefGoogle Scholar
• 2c Byers PK. Canty AJ. Skelton BW. White AH. J. Chem. Soc., Chem. Commun.  1987,  1093 
  CrossrefGoogle Scholar
• 2d Byers PK. Canty AJ. Skelton BW. White AH. Organometallics  1990,  9:  826 
  CrossrefGoogle Scholar
• 2e Brown DG. Byers PK. Canty AJ. Organometallics  1990,  9:  1231 
  CrossrefGoogle Scholar
• 2f Canty AJ. Minchin NJ. Engelhardt LM. Skelton BW. White AH. J. Chem. Soc., Dalton Trans.  1986,  645 
  CrossrefGoogle Scholar
• 2g McGarvey JJ. Toftlund H. Al-Obaidi AHR. Taylor KP. Bell SEJ. Inorg. Chem.  1993,  32:  2469 
  CrossrefGoogle Scholar
• 2h Clark HC. Ferguson G. Jain VK. Parvezm M. J. Organomet. Chem.  1984,  270:  365 
  CrossrefGoogle Scholar
• 2i Clark HC. Mesubi MA. J. Organomet. Chem.  1981,  215:  131 
  CrossrefGoogle Scholar
• 2j Barqawi KR. Llobet A. Meyer TJ. J. Am. Chem. Soc.  1988,  110:  7751 
  CrossrefGoogle Scholar
• 2k Llobet A. Doppelt P. Meyer TJ. Inorg. Chem.  1988,  27:  514 
  CrossrefGoogle Scholar
• 2l Llobet A. Curry ME. Evans HT. Meyer TJ. Inorg. Chem.  1989,  28:  3131 
  CrossrefGoogle Scholar
• 2m Fernandez-Baeza J. Jalon FA. Otero A. Rodrigo-Blanco ME. J. Chem. Soc., Dalton Trans.  1995,  1015 
  CrossrefGoogle Scholar
• 2n Astley T. Gulbis JM. Hitchman MA. Tiekink RT. J. Chem. Soc., Dalton Trans.  1993,  509 
  CrossrefGoogle Scholar
• 2o Byers PK. Stone FGA. J. Chem. Soc., Dalton Trans.  1991,  93 
  CrossrefGoogle Scholar
• 2p Onishi M. Sugimura K. Hiraki K. Bull. Chem. Soc. Jpn.  1978,  51:  3209 
  CrossrefGoogle Scholar
• 2q O’Sullivan DJ. Lalor FJ. J. Organomet. Chem.  1973,  57:  C58 
  CrossrefGoogle Scholar
• 2r Dhawan IK. Bruck MA. Schilling B. Grittini C. Enemark JH. Inorg. Chem.  1995,  34:  3801 
  CrossrefGoogle Scholar
• 2s Bhambri S. Tocher DA. J. Chem. Soc., Dalton Trans.  1997,  3367 
  CrossrefGoogle Scholar
• 2t Lobbia GG. Leonesi D. Cingolani A. Lorenzotti A. Bonati F. Synth. React. Inorg. Met.-Org. Chem.  1987,  17:  909 
  CrossrefGoogle Scholar
• 2u Lobbia GG. Bonati F. Cingolani A. Leonesi D. Synth. React. Inorg. Met.-Org. Chem.  1989,  19:  827 
  CrossrefGoogle Scholar
• 2v Pettinari C. Santini C. Leonesi D. Polyhedron  1994,  13:  1553 
  CrossrefGoogle Scholar
• 3 Trofimenko S. J. Am. Chem. Soc.  1970,  92:  5118 
  CrossrefGoogle Scholar
• 4a

  Byers, P. K.; Canty, A. J.; Honeyman, R. T. Inorg. Synth. 2002 , submitted.

  Crossref
• 4b Byers PK. Canty AJ. Organometallics  1990,  9:  210 
  CrossrefGoogle Scholar
• 4c Byers PK. Canty AJ. Honeyman RT. J. Organomet. Chem.  1990,  385:  417 
  CrossrefGoogle Scholar
• 4d Canty AJ. Honeyman RT. J. Organomet. Chem.  1990,  387:  247 
  CrossrefGoogle Scholar
• 4e Canty AJ. Honeyman RT. Skelton BW. White AH. J. Organomet. Chem.  1990,  389:  277 
  CrossrefGoogle Scholar
• 4f Canty AJ. Honeyman RT. Skelton BW. White AH. J. Chem. Soc., Dalton Trans.  1992,  2663 
  CrossrefGoogle Scholar
• 5 Reger DL. Grattan TC. Brown KJ. Little CA. Lamba JJS. Rheingold AL. Sommer RD. J. Organomet. Chem.  2000,  607:  120 
  CrossrefGoogle Scholar
• 6a Reger DL. Semeniuc RF. Smith MD. J. Chem. Soc., Dalton Trans.  2002,  476 
  CrossrefGoogle Scholar
• 6b Martini D. Pellei M. Pettinari C. Skelton BW. White AH. Inorg. Chim. Acta  2002,  333:  72 
  CrossrefGoogle Scholar
• 6c Reger DL. Semeniuc RF. Smith MD. Inorg. Chem. Commun.  2002,  5:  278 
  CrossrefGoogle Scholar
• 6d Reger DL. Semeniuc RF. Smith MD. Eur. J. Inorg. Chem.  2002,  543 
  CrossrefGoogle Scholar
• 6e Fiel d LD. Messerle BA. Soler LP. Hambley TW. Turner P. J. Organomet. Chem.  2002,  655:  146 
  CrossrefGoogle Scholar
• 6f Cingolani A. Effendy Martini D. Pellei M. Pettinari C. Skelton BW. White AH. Inorg. Chim. Acta  2002,  328:  87 
  CrossrefGoogle Scholar
• 6g Reger DL. Wright TD. Semeniuc RF. Grattan TC. Smith MD. Inorg. Chem.  2001,  40:  6212 
  CrossrefGoogle Scholar
• 6h Reger DL. Semeniuc RF. Smith MD. Inorg. Chem.  2001,  40:  6545 
  CrossrefGoogle Scholar
• 6i Cvetkovic M. Batten SR. Moubarki B. Murray KS. Spiccia L. Inorg. Chim. Acta  2001,  324:  131 
  CrossrefGoogle Scholar
• 6j Santos AM. Kühn FE. Bruus-Jensen K. Lucas I. Romão CC. Herdtweck E. J. Chem. Soc., Dalton Trans.  2001,  1332 
  CrossrefGoogle Scholar
• 6k Field LD. Messerle BA. Soler L. Buys IE. Hambley TW. J. Chem. Soc., Dalton Trans.  2001,  1959 
  CrossrefGoogle Scholar
• 6l Anderson PA. Astley T. Hitchman MA. Keene R. Moubaraki B. Murray KS. Skelton BW. Tiekink ERT. Totlund H. White AH. J. Chem. Soc., Dalton Trans.  2000,  3505 
  CrossrefGoogle Scholar
• 6m Pettinari C. Pellei M. Cingolani A. Martini D. Drozdov A. Troyanov S. Panzeri W. Mele A. Inorg. Chem.  1999,  38:  5777 
  CrossrefGoogle Scholar
• 7a Katritzky AR. Abdel-Rahman AE. Leahy DE. Schwarz OA. Tetrahedron  1983,  39:  4133 
  CrossrefGoogle Scholar
• 7b Byers PK. Canty AJ. Honeyman RT. Claremont RM. Lopez C. Lavandera JL. Elguero J. Gazz. Chim. Ital.  1992,  122:  341 
  CrossrefGoogle Scholar
• 7c Esteruelas MA. Oro LA. Claramunt RM. Lopez C. Lavandera JL. Elguero J. J. Organomet. Chem.  1989,  366:  245 
  CrossrefGoogle Scholar
• 8 Otero A. Fernandez-Baeza J. Tejeda J. Antinolo A. Carrillo-Hermosilla F. Diez-Barra E. Lara-Sanchez A. Fernandez-Lopez M. Lanfranchi M. Pellinghelli MA. J. Chem. Soc., Dalton Trans.  1999,  3537 
  CrossrefGoogle Scholar
• 9 Kläui W. Berghahn M. Rheinwald G. Lang H. Angew. Chem. Int. Ed.  2000,  39:  2464 
  CrossrefGoogle Scholar
• 10 Reger DL. Little CA. Rheingold AL. Lam M. Liable-Sands LM. Rhagitan B. Concolino T. Mohan A. Long GJ. Briois V. Grandjean F. Inorg. Chem.  2001,  40:  1508 
  CrossrefGoogle Scholar
• 13 Lawrence SC. Skinner ME. Green JC. Mountford P. Chem. Commun.  2001,  705 
  CrossrefGoogle Scholar

Reger, D. L.; Little C. A. unpublished results.

Baker, M. V. personal communication.