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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Reactivity of β-Diketiminato Magnesium Alkyl Complexes: Heterocumulenes and Phosphanes*

Morgan J. Taylor A , Martyn P. Coles A B and J. Robin Fulton A B C
+ Author Affiliations
- Author Affiliations

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

B Current address: School of Chemical and Physical Sciences, Victoria University of Wellington, Wellington 6012, NZ.

C Corresponding author. Email: j.robin.fulton@vuw.ac.nz

Australian Journal of Chemistry 68(4) 635-640 https://doi.org/10.1071/CH14526
Submitted: 28 August 2014  Accepted: 26 October 2014   Published: 24 March 2015

Abstract

Heteroleptic β-diketiminate/amidinate magnesium complexes {(BDI)Mg[MeC(NCy)2]} and {(BDI)Mg[BnC(NCy)2]} (Bn = CH2C6H5; BDI = {[N(2,6-iPr2C6H3)C(Me)]2CH}) were synthesised by treatment of [(BDI)MgR(THF)] (R = Me, Bn) with dicyclohexylcarbodiimide. Rare terminal magnesium phosphanide complexes [(BDI)Mg(PR′2)(THF)] (R′ = Cy, Ph) were synthesised through prolonged exposure of [(BDI)MgMe(THF)] with di-substituted phosphines. Spectroscopic and structural details of these complexes will be discussed.


References

[1]  P. J. Bailey, C. M. E. Dick, S. Fabre, S. Parsons, J. Chem. Soc., Dalton Trans. 2000, 1655.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXksFWms7Y%3D&md5=ff25612e65a436080a104ed469965255CAS |

[2]  V. C. Gibson, J. A. Segal, A. J. P. White, D. J. Williams, J. Am. Chem. Soc. 2000, 122, 7120.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXks1ehtL4%3D&md5=f28b9791d4f1e34af007e041a118397dCAS |

[3]  M. H. Chisholm, J. Gallucci, K. Phomphrai, Inorg. Chem. 2002, 41, 2785.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XjtVyhs7o%3D&md5=60f230cf730f3cf12811637446eefe24CAS | 12005504PubMed |

[4]  A. P. Dove, V. C. Gibson, E. L. Marshall, A. J. P. White, D. J. Williams, Chem. Commun. 2002, 1208.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XjslalsbY%3D&md5=39a75a957979e04b9fd0f8b881c2c07bCAS |

[5]  H. J. Hao, H. W. Roesky, Y. Q. Ding, C. M. Cui, M. Schormann, H. G. Schmidt, M. Noltemeyer, B. Zemva, J. Fluorine Chem. 2002, 115, 143.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xktlyhs70%3D&md5=cd502a0de69fd190d5411ecf35ee84eeCAS |

[6]  L. F. Sánchez-Barba, D. L. Hughes, S. M. Humphrey, M. Bochmann, Organometallics 2006, 25, 1012.
         | Crossref | GoogleScholarGoogle Scholar |

[7]  P. I. Bailey, S. T. Liddle, C. A. Morrison, S. Parsons, Angew. Chem., Int. Ed. 2001, 40, 4463.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXptlWhtb8%3D&md5=8f13dca2f2bf74b0e3685783a231be52CAS |

[8]  S. P. Green, C. Jones, A. Stasch, Science 2007, 318, 1754.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhsVWhu7nL&md5=a55e9ee1e379de060d65cedfda161bebCAS | 17991827PubMed |

[9]  S. P. Green, C. Jones, A. Stasch, Angew. Chem., Int. Ed. 2008, 47, 9079.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhsVCnsbzO&md5=d84478edd0da0d3a4b557d4e41643542CAS |

[10]  S. J. Bonyhady, S. P. Green, C. Jones, S. Nembenna, A. Stasch, Angew. Chem., Int. Ed. 2009, 48, 2973.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXkvVekurs%3D&md5=1fc58162bfb26ca66f0c7093b39eadaeCAS |

[11]  A. Stasch, C. Jones, Dalton Trans. 2011, 40, 5659.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXmsVagtb4%3D&md5=31177de8ff027ef778f6efaf46d95c99CAS | 21390353PubMed |

[12]  R. Lalrempuia, A. Stasch, C. Jones, Chem. Sci. 2013, 4, 4383.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhs1yis77M&md5=5421ce3508b96c7273722107f44e25d4CAS |

[13]  J. Spielmann, M. Bolte, S. Harder, Chem. Commun. 2009, 6934.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhtl2iu7zK&md5=3959613613691338c2e43f508d32613cCAS |

[14]  J. Spielmann, D. F. J. Piesik, S. Harder, Chem. – Eur. J. 2010, 16, 8307.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXptlejt7w%3D&md5=a669544cdfd9cb3b29f76ff42b62610aCAS | 20564288PubMed |

[15]  C. Jones, S. J. Bonyhady, S. Nembenna, A. Stasch, Eur. J. Inorg. Chem. 2012, 2596.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xkslakur4%3D&md5=f3b6f676e70a5e1efb6ef951efe88eebCAS |

[16]  R. A. Collins, J. Unruangsri, P. Mountford, Dalton Trans. 2013, 42, 759.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhvVajtrrF&md5=5f628b41f859baed372a433e94fb6648CAS | 23132175PubMed |

[17]  M. Arrowsmith, M. S. Hill, G. Kociok-Kohn, Chem – Eur. J. 2013, 19, 2776.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXntFWrug%3D%3D&md5=4a707493d0c5dd50b2e13e58c6212d5bCAS | 23307492PubMed |

[18]  M. R. Crimmin, M. Arrowsmith, A. G. M. Barrett, I. J. Casely, M. S. Hill, P. A. Procopiou, J. Am. Chem. Soc. 2009, 131, 9670.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXns1Onsr0%3D&md5=4b843c6bdb4e49111844b064b1789743CAS | 19552442PubMed |

[19]  L. A. M. Harris, M. P. Coles, J. R. Fulton, Inorg. Chim. Acta 2011, 369, 97.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXksV2rtr0%3D&md5=c6909674bc642fa39ce83c9e68913ed6CAS |

[20]  L. Ferro, P. B. Hitchcock, M. P. Coles, H. Cox, J. R. Fulton, Inorg. Chem. 2011, 50, 1879.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXlsV2jsQ%3D%3D&md5=1109bbadd6279eeaa302d3d11d0cd139CAS | 21229976PubMed |

[21]  L. A. M. Harris, E. C. Y. Tam, M. P. Coles, J. R. Fulton, Dalton Trans. 2014, 43, 13803.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhtlCjtbfK&md5=ee976591bbf422cff3717e4942a82bdeCAS |

[22]  M. S. Hill, D. J. MacDougall, M. F. Mahon, Dalton Trans. 2010, 39, 11129.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsVaqur%2FI&md5=7a032d08975cb77e3eb8d8dcdeace9eeCAS | 20959940PubMed |

[23]  M. S. Hill, G. Kociok-Kohn, D. J. MacDougall, M. F. Mahon, C. Weetman, Dalton Trans. 2011, 40, 12500.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhsVyrsbfJ&md5=745e29ca28bc56990c1b2e7269f19543CAS | 21986998PubMed |

[24]  J. Prust, K. Most, I. Muller, E. Alexopoulos, A. Stasch, I. Uson, H. W. Roesky, Z. Anorg. Allg. Chem. 2001, 627, 2032.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXlvV2qsbw%3D&md5=9294cfa076eaa9d834761b149c902022CAS |

[25]  S. E. Baillie, V. L. Blair, T. D. Bradley, W. Clegg, J. Cowan, R. W. Harrington, A. Hernan-Gomez, A. R. Kennedy, Z. Livingstone, E. Hevia, Chem. Sci. 2013, 4, 1895.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXjtlyms7k%3D&md5=e5e0dd58da84ab4dc314adbab4da6cbaCAS |

[26]  A. R. Sadique, M. J. Heeg, C. H. Winter, Inorg. Chem. 2001, 40, 6349.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXosFWqsLY%3D&md5=f22682577e84533abc1e0f5508497e0cCAS | 11720486PubMed |

[27]  R. J. Schwamm, M. P. Coles, Organometallics 2013, 32, 5277.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhsVyls7zL&md5=92fe998e1fcf035996c3df7e893f9f53CAS |

[28]  A. P. Dove, V. C. Gibson, P. Hormnirun, E. L. Marshall, J. A. Segal, A. J. P. White, D. J. Williams, Dalton Trans. 2003, 3088.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXls1Oltbs%3D&md5=992ab8598fd50c3b02cc99531753dc59CAS |

[29]  T. Chivers, M. C. Copsey, C. Fedorchuk, M. Parvez, M. Stubbs, Organometallics 2005, 24, 1919.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXitlSju7c%3D&md5=fe193a9ab172eec4b49079b7015b5b58CAS |

[30]  B. M. Day, W. Knowelden, M. P. Coles, Dalton Trans. 2012, 41, 10930.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xht1Kmt7zO&md5=e07249f9402d46376b9ba26f9c0513c6CAS | 22886325PubMed |

[31]  N. Nimitsiriwat, V. C. Gibson, E. L. Marshall, P. Takolpuckdee, A. K. Tomov, A. J. P. White, D. J. Williams, M. R. J. Elsegood, S. H. Dale, Inorg. Chem. 2007, 46, 9988.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtFegs77N&md5=1ce8a4664a95492d06a7ef838059810fCAS | 17927169PubMed |

[32]  J. A. R. Schmidt, J. Arnold, J. Chem. Soc., Dalton Trans. 2002, 2890.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xlt1OjtLg%3D&md5=7a1a013892616712a0be05d53b02aacbCAS |

[33]  M. Chen, J. R. Fulton, P. B. Hitchcock, N. C. Johnstone, M. F. Lappert, A. V. Protchenko, Dalton Trans. 2007, 2770.
         | Crossref | GoogleScholarGoogle Scholar | 17592593PubMed |

[34]  Z. B. Maksić, B. Kovacevic, J. Chem. Soc., Perkin Trans. 2 1999, 2623.
         | Crossref | GoogleScholarGoogle Scholar |

[35]  M. R. Crimmin, A. G. M. Barrett, M. S. Hill, P. B. Hitchcock, P. A. Procopiou, Organometallics 2007, 26, 2953.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXksl2ru78%3D&md5=8619c054a82fa36aef2a5a306884a2e9CAS |

[36]  R. E. Mulvey, K. Wade, D. R. Armstrong, G. T. Walker, R. Snaith, W. Clegg, et al. Polyhedron 1987, 6, 987.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2sXkvVyntrc%3D&md5=8994acf81086cd09f15bf3832bf75eeeCAS |

[37]  E. Hey, L. M. Engelhardt, C. L. Raston, A. H. White, Angew. Chem., Int. Ed. Engl. 1987, 26, 81.
         | Crossref | GoogleScholarGoogle Scholar |

[38]  M. Westerhausen, A. Pfitzner, J. Organomet. Chem. 1995, 487, 187.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXjtlOksLc%3D&md5=8dc78895c29c8c5f9bc158285c402bf4CAS |

[39]  B. Srinivas, C. C. Chang, C. H. Chen, M. Y. Chiang, I. T. Chen, Y. Wang, G. H. Lee, J. Chem. Soc., Dalton Trans. 1997, 957.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXisFCmt78%3D&md5=181688698dcf4c87e96c5db6d0f44a29CAS |

[40]  M. D. Li, C. C. Chang, Y. Wang, G. H. Lee, Organometallics 1996, 15, 2571.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28XisVGrt78%3D&md5=5156e056efce88519735937621247334CAS |

[41]  Y. Yu, A. R. Sadique, J. M. Smith, T. R. Dugan, R. E. Cowley, W. W. Brennessel, C. J. Flaschenriem, E. Bill, T. R. Cundari, P. L. Holland, J. Am. Chem. Soc. 2008, 130, 6624.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXlt1Ggs7c%3D&md5=ce9517692ad762aa9150cd9508376bdaCAS | 18444648PubMed |

[42]  W. H. Monillas, G. P. A. Yap, K. H. Theopold, J. Chem. Crystallogr. 2009, 39, 849.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhtFelsLjF&md5=130d18530bf921aef21d381341a42e23CAS |

[43]  M. Westerhausen, W. Schwarz, Z. Anorg. Allg. Chem. 1994, 620, 304.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXjtFCgtbs%3D&md5=095706dd563fd1171400b57e8c57d07bCAS |

[44]  M. Westerhausen, M. H. Digeser, B. Wieneke, H. Noth, J. Knizek, Eur. J. Inorg. Chem. 1998, 517.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXitFOkur4%3D&md5=af604a82644d3193fa402d0d2fd28f35CAS |

[45]  S. Blair, K. Izod, W. Clegg, R. W. Harrington, Eur. J. Inorg. Chem. 2003, 3319.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXotFSkuro%3D&md5=8bbfd58b132740d0ce7d35088d9414d8CAS |

[46]  B. M. Day, M. P. Coles, Eur. J. Inorg. Chem. 2010, 5471.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsVyrsbrE&md5=afa0d200a0ab5bc19330d6defd99d7aeCAS |

[47]  E. C. Y. Tam, N. A. Maynard, D. C. Apperley, J. D. Smith, M. P. Coles, J. R. Fulton, Inorg. Chem. 2012, 51, 9403.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xht1Wqur3J&md5=9a0ab52c136bfe4ae258b431bb82b0edCAS |

[48]  P. L. Bailey, R. A. Coxall, C. M. Dick, S. Fabre, L. C. Henderson, C. Herber, S. T. Liddle, D. Lorono-Gonzalez, A. Parkin, S. Parsons, Chem. – Eur. J. 2003, 9, 4820.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXot1yksbc%3D&md5=d5f12e67720aca5a5601bcb85cf8c2c4CAS |

[49]  G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, 64, 112.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhsVGhurzO&md5=59f548f8f29686b585f885edea91b42eCAS |

[50]  S. J. Coles, P. A. Gale, Chem. Sci. 2012, 3, 683.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhslOqs7k%3D&md5=0b89c734c2ab06f3fe0d6622845a9bd2CAS |