Free Standard AU & NZ Shipping For All Book Orders Over $80!
Register      Login
Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
Shopping Cart: ( empty )
You are here: Home > Journals > CH > CH12560
RESEARCH ARTICLE
Contents Vol 66(10)

Bicyclic Guanidinates in Mono- and Di-Valent Metal Complexes, Including Group 1/2 and Group 1/12 Heterometallic Systems

Martyn P. Coles A C and Peter B. Hitchcock B
+ Author Affiliations
- Author Affiliations

A School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington 6012, New Zealand.

B Department of Chemistry, University of Sussex, Falmer, Brighton BN1 9QJ, UK.

C Corresponding author. Email: martyn.coles@vuw.ac.nz

Australian Journal of Chemistry 66(10) 1124-1130 https://doi.org/10.1071/CH12560
Submitted: 20 December 2012  Accepted: 30 January 2013   Published: 27 February 2013

Abstract

Complexes containing mono-, di-, and mixed mono-/di-valent metal centres supported by the [hpp]– anion (hppH = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) are reported. Amine elimination from Mn(N{SiMe3}2)2 using the neutral guanidine is a clean route to the heteroleptic compound [Mn(hpp)(N{SiMe3}2)]2. Addition of 18-crown-6 to a solution of the hpp– potassium salt (hppK) enables the first potassium derivative of [hpp]– to be structurally analysed, showing that the crown ether restricts aggregation to afford a monometallic structure. Mixed lithium–magnesium and lithium–zinc compounds of general formula Li2M2(hpp)6 (M = Mg, Zn) have been characterised crystallographically showing the guanidinate anions to be present in two different coordination modes, bridging two- or four-metal centres. Spectroscopic measurements suggest a robust framework that is maintained in solution.


References

[1]  (a) R. E. Mulvey, Acc. Chem. Res. 2009, 42, 743.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXktFemurY%3D&md5=24be6929dd0bde5196cafeff5f4c1bffCAS |
      (b) R. E. Mulvey, Organometallics 2006, 25, 1060.
         | Crossref | GoogleScholarGoogle Scholar |

[2]  (a) E. Hevia, D. J. Gallagher, A. R. Kennedy, R. E. Mulvey, C. T. O’Hara, C. Talmard, Chem. Commun. 2004, 2422.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXptFaqsrs%3D&md5=aa23b713840c2a7ffe51084151390861CAS |
      (b) D. R. Armstrong, W. Clegg, S. H. Dale, D. V. Graham, E. Hevia, L. M. Hogg, G. W. Honeyman, A. R. Kennedy, R. E. Mulvey, Chem. Commun. 2007, 598.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) P. C. Andrikopoulos, D. R. Armstrong, H. R. L. Barley, W. Clegg, S. H. Dale, E. Hevia, G. W. Honeyman, A. R. Kennedy, R. E. Mulvey, J. Am. Chem. Soc. 2005, 127, 6184.
         | Crossref | GoogleScholarGoogle Scholar |

[3]  L. M. Carrella, W. Clegg, D. V. Graham, L. M. Hogg, A. R. Kennedy, J. Klett, R. E. Mulvey, E. Rentschler, L. Russo, Angew. Chem. Int. Ed. 2007, 46, 4662.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXnsVWitrk%3D&md5=6593ef4ff8cbfa4b3a0a2bc27d4ff0eeCAS |

[4]  (a) P. C. Andrikopoulos, D. R. Armstrong, D. V. Graham, E. Hevia, A. R. Kennedy, R. E. Mulvey, C. T. O’Hara, C. Talmard, Angew. Chem. Int. Ed. 2005, 44, 3459.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXlsV2ju7g%3D&md5=1d8810cf7762aff84e9f0c946a00fc0eCAS |
      (b) V. L. Blair, L. M. Carrella, W. Clegg, B. Conways, R. W. Harrington, L. M. Hogg, J. Klett, R. E. Mulvey, E. Rentschler, L. Russo, Angew. Chem. Int. Ed. 2008, 47, 6208.
         | Crossref | GoogleScholarGoogle Scholar |

[5]  K. W. Henderson, A. R. Kennedy, R. E. Mulvey, C. T. O’Hara, R. B. Rowlings, Chem. Commun. 2001, 1678.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXmtVeit7Y%3D&md5=9e59f8dc5cdabcac1d7fcf378bfa8501CAS |

[6]  F. García, M. McPartlin, J. V. Morey, D. Nobuto, Y. Kondo, H. Naka, M. Uchiyama, A. E. H. Wheatley, Eur. J. Org. Chem. 2008, 644.
         | Crossref | GoogleScholarGoogle Scholar |

[7]  W. Clegg, S. H. Dale, A. M. Drummond, E. Hevia, G. W. Honeyman, R. E. Mulvey, J. Am. Chem. Soc. 2006, 128, 7434.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XkslKhtrk%3D&md5=5de0ad021827afd7e7c46dfeacac7d24CAS |

[8]  S. E. Baillie, V. L. Blair, D. C. Blakemore, D. Hay, A. R. Kennedy, D. C. Pryde, E. Hevia, Chem. Commun. 2012, 48, 1985.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XovFyktw%3D%3D&md5=3f4b95dd1299ac96566c9ba26d39e039CAS |

[9]  (a) J. Barker, M. Kilner, Coord. Chem. Rev. 1994, 133, 219.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXlvFCjtbY%3D&md5=8fc2de5ace26f90617d44bf0c62c37d6CAS |
      (b) F. T. Edelmann, Coord. Chem. Rev. 1994, 137, 403.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) F. T. Edelmann, Top. Curr. Chem. 1996, 179, 113.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) P. C. Junk, M. L. Cole, Chem. Commun. 2007, 1579.
         | Crossref | GoogleScholarGoogle Scholar |

[10]  (a) P. J. Bailey, S. Pace, Coord. Chem. Rev. 2001, 214, 91.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXhslemsbg%3D&md5=0f1d8ebe68223ff2205fe47bb1dab55dCAS |
      (b) F. T. Edelmann, Adv. Organomet. Chem. 2008, 57, 183.
         | Crossref | GoogleScholarGoogle Scholar |

[11]  M. P. Coles, Chem. Commun. 2009, 3659.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXnslentLw%3D&md5=54e795297f53a216668aaa05073b36a3CAS |

[12]  (a) S. R. Boss, M. P. Coles, R. Haigh, P. B. Hitchcock, R. Snaith, A. E. H. Wheatley, Angew. Chem. Int. Ed. 2003, 42, 5593.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXpsl2ksLw%3D&md5=4fd958bf1c0d11c4cd034fd7635abd49CAS |
      (b) S. R. Boss, M. P. Coles, V. Eyre-Brook, F. García, R. Haigh, P. B. Hitchcock, M. McPartlin, J. V. Morey, H. Naka, P. R. Raithby, H. A. Sparkes, C. W. Tate, A. E. H. Wheatley, Dalton Trans. 2006, 5574.
         | Crossref | GoogleScholarGoogle Scholar |

[13]  M. P. Coles, P. B. Hitchcock, Chem. Commun. 2005, 3165.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXltlKht70%3D&md5=b05ab10c4a489dc27f0cfa8b76f7c7b7CAS |

[14]  D. Woodruff, M. Bodensteiner, D. O. Sells, R. E. P. Winpenny, R. A. Layfield, Dalton Trans. 2011, 40, 10918.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtlShu73L&md5=41c3ac2eec9185b935e9324d6d262653CAS |

[15]  M. P. Coles, P. B. Hitchcock, Eur. J. Inorg. Chem. 2004, 2662.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXlvVKjsrw%3D&md5=ae466b15da27238331ca26bbee567190CAS |

[16]  B. M. Day, N. E. Mansfield, M. P. Coles, P. B. Hitchcock, Chem. Commun. 2011, 47, 4995.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXkslKit7c%3D&md5=970dc64f9dd91a4e7d034d0f41802eddCAS |

[17]  (a) D. Rudolf, G. Storch, E. Kaifer, H.-J. Himmel, Eur. J. Inorg. Chem. 2012, 2368.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XksV2nsbc%3D&md5=20f092598116e22fd759f08dad0d9208CAS |
      (b) O. Ciobanu, A. Fuchs, M. Reinmuth, A. Lebkucher, E. Kaifer, H. Wadepohl, H.-J. Himmel, Z. Anorg. Allg. Chem. 2010, 636, 543.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) G. Robinson, C. Y. Tang, R. Koppe, A. R. Cowley, H.-J. Himmel, Chem.–Eur. J. 2007, 13, 2648.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) S. L. Aeilts, M. P. Coles, D. C. Swenson, R. F. Jordan, V. G. Young, Organometallics 1998, 17, 3265.
         | Crossref | GoogleScholarGoogle Scholar |

[18]  S. J. Birch, S. R. Boss, S. C. Cole, M. P. Coles, R. Haigh, P. B. Hitchcock, A. E. H. Wheatley, Dalton Trans. 2004, 3568.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXovFOhsbw%3D&md5=43f390fe58e8b2e3bda3e2d80bebd800CAS |

[19]  S. A. Sulway, D. Collison, J. J. W. McDouall, F. Tuna, R. A. Layfield, Inorg. Chem. 2011, 50, 2521.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhvFWju70%3D&md5=6e3ca158cac9164862b02896fd39f950CAS |

[20]  F. A. Cotton, C. A. Murillo, D. J. Timmons, Polyhedron 1998, 18, 423.
         | Crossref | GoogleScholarGoogle Scholar |

[21]  W. Clegg, B. Conway, E. Hevia, M. D. McCall, L. Russo, R. E. Mulvey, J. Am. Chem. Soc. 2009, 131, 2375.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXht1Ohurw%3D&md5=1e2c56134bc79f311bc9d176f9212166CAS |

[22]  R. A. Andersen, K. Faegri, J. C. Green, A. Haaland, M. F. Lappert, W.-P. Leung, K. Rypdal, Inorg. Chem. 1988, 27, 1782.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXitFGhtb8%3D&md5=cd43888b34d1a6866528ead7fc72c2cfCAS |

[23]  R. A. Layfield, Chem. Soc. Rev. 2008, 37, 1098.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXmtlSisLg%3D&md5=607b70a2c506594bba68ae91129b78ffCAS |

[24]  (a) J. Garcia-Álvarez, A. R. Kennedy, J. Klett, R. E. Mulvey, Angew. Chem. Int. Ed. 2007, 46, 1105.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) V. L. Blair, L. M. Carrella, W. Clegg, B. Conway, R. W. Harrington, L. M. Hogg, J. Klett, R. E. Mulvey, E. Rentschler, L. Russo, Angew. Chem. Int. Ed. 2008, 47, 6208.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) V. L. Blair, W. Clegg, B. Conway, E. Hevia, A. R. Kennedy, J. Klett, R. E. Mulvey, L. Russo, Chem.–Eur. J. 2008, 14, 65.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) V. L. Blair, L. M. Carrella, W. Clegg, J. Klett, R. E. Mulvey, E. Rentschler, L. Russo, Chem.–Eur. J. 2009, 15, 856.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) V. L. Blair, W. Clegg, R. E. Mulvey, L. Russo, Inorg. Chem. 2009, 48, 8863.
         | Crossref | GoogleScholarGoogle Scholar |

[25]  C. Brinkmann, F. García, J. V. Morey, M. McPartlin, S. Singh, A. E. H. Wheatley, D. S. Wright, Dalton Trans. 2007, 1570.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXktVSjs7o%3D&md5=1463add78c1c6842510ea0cb353b3e4cCAS |

[26]  S. H. Oakley, D. B. Soria, M. P. Coles, P. B. Hitchcock, Polyhedron 2006, 25, 1247.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XitVens74%3D&md5=2ecf1feadb219b01865f6f0476591e74CAS |

[27]  G. Häfelinger, K. H. Kuske, The Chemistry of the Amindines and Imidates 1991, Vol. 2, Ch. 1 (Wiley: Chichester).

[28]  C. Neuhäuser, M. Reinmouth, E. Kaifer, H.-J. Himmel, Eur. J. Inorg. Chem. 2012, 1250.
         | Crossref | GoogleScholarGoogle Scholar |

[29]  (a) W. J. Evans, E. Montalvo, J. W. Ziller, A. G. DiPasquale, A. L. Rheingold, Inorg. Chem. 2010, 49, 222.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsFSrsbrK&md5=66af91ffe9943ffe72932b61e1ac3facCAS |
      (b) J. F. Berry, F. A. Cotton, P. Huang, C. A. Murillo, X. Wang, Dalton Trans. 2005, 3713.
         | Crossref | GoogleScholarGoogle Scholar |

[30]  G. R. Giesbrecht, A. Shafir, J. Arnold, J. Chem. Soc., Dalton Trans. 1999, 3601.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXms1Cmt7c%3D&md5=92b8e0a62e890cb369f6af2f4e03df2dCAS |

[31]  G. Jin, C. Jones, P. C. Junk, K.-A. Lippert, R. P. Rose, A. Stasch, New J. Chem. 2009, 33, 64.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhsFelsrvF&md5=7c458c9ea974fe73c64673bf82967e8dCAS |

[32]  (a) P. Benndorf, C. Preuß, P. W. Roesky, J. Organomet. Chem. 2011, 696, 1150.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXjsFartbo%3D&md5=4e9d4229835635cf614dadbb352f3957CAS |
      (b) M. L. Cole, A. J. Davies, C. Jones, P. C. Junk, J. Organomet. Chem. 2007, 692, 2508.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) M. L. Cole, D. J. Evans, P. C. Junk, M. K. Smith, Chem.–Eur. J. 2003, 9, 415.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) M. L. Cole, P. C. Junk, J. Organomet. Chem. 2003, 666, 55.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) J. Baldamus, C. Berghof, M. L. Cole, D. J. Evans, E. Hey-Hawkins, P. C. Junk, J. Chem. Soc., Dalton Trans. 2002, 4185.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) J. Baldamus, C. Berghof, M. L. Cole, D. J. Evans, E. Hey-Hawkins, P. C. Junk, J. Chem. Soc., Dalton Trans. 2002, 2802.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) P. B. Hitchcock, M. F. Lappert, M. Layh, J. Chem. Soc., Dalton Trans. 1998, 3113.
         | Crossref | GoogleScholarGoogle Scholar |
      (h) P. B. Hitchcock, M. F. Lappert, D.-S. Liu, J. Organomet. Chem. 1995, 488, 241.
         | Crossref | GoogleScholarGoogle Scholar |

[33]  G. M. Sheldrick, SHELXL-97: Program for the Refinement of Crystal Structures 1997 (University of Göttingen: Göttingen).