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Australian Journal of Chemistry Australian Journal of Chemistry Society
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REVIEW

A Magic Equation: Delta Bonds Plus Bicyclic Guanidinates Equals Strong Reducing Agents*

Carlos A. Murillo
+ Author Affiliations
- Author Affiliations

Department of Chemistry, PO Box 3012, Texas A&M University, College Station, Texas 77842-3012, USA. Email: murillo@tamu.edu




Carlos A. Murillo studied chemistry at the University of Costa Rica and Texas A&M University where he received his Ph.D. in 1973 with F. Albert Cotton. He then did postdoctoral work with Malcolm H. Chisholm at Princeton University. He went back to Costa Rica where he quickly rose to the rank of Professor. In 1991, he moved to Texas A&M University as Executive Director of the Laboratory for Molecular Structure and Bonding, and in 2007 he took a position as Program Director in the Division of Chemistry at the US National Science Foundation. He has continued his research as an adjunct professor at Texas A&M University and the University of Texas at El Paso. He is a Fellow of the American Association for the Advancement of Science (AAAS) and a charter member of the Costa Rican Academy of Sciences.

Australian Journal of Chemistry 67(7) 972-979 https://doi.org/10.1071/CH13694
Submitted: 14 December 2013  Accepted: 31 January 2014   Published: 3 March 2014

Abstract

Reactions of bicyclic guanidinates with dimolybdenum and ditungsten precursors having quadruple bonded units with a σ2π4δ2 (Q) electronic configuration have generated the most easily ionized, chemically stable species and very strong reducing agents. Analogous rhenium compounds have led to the formation of species having dimetal units in unusually high oxidation states. Here we review this chemistry and the accounts that explain such behaviour that has been attributed to the interaction of the π electrons of the guanidinate C(N)3 core with the electrons that give rise to the delta bond of the dimetal units.


References

[1]  (a) See for example: S. R. Foley, G. P. A. Yap, D. S. Richeson, Polyhedron 2002, 21, 619.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xis1yjt74%3D&md5=942ccb5bed9479a5dda2b8de5020c4acCAS |
      (b) D. B. Soria, J. Grundy, M. P. Coles, P. B. Hitchcock, J. Organomet. Chem. 2005, 690, 2278.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) M. P. Coles, P. B. Hitchcock, Organometallics 2003, 22, 5201.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) M. P. Coles, P. B. Hitchcock, Dalton Trans. 2001, 1169.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) M. P. Coles, P. B. Hitchcock, Inorg. Chim. Acta 2004, 357, 4330.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) S. H. Oakley, M. P. Coles, P. B. Hitchcock, Inorg. Chem. 2004, 43, 7564.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) M. P. Coles, P. B. Hitchcock, Eur. J. Inorg. Chem. 2004, 2662.
         | Crossref | GoogleScholarGoogle Scholar |
      (h) M. S. Khalaf, M. P. Coles, P. B. Hitchcock, Dalton Trans. 2008, 4288.
         | Crossref | GoogleScholarGoogle Scholar |
      (i) M. D. Irwin, H. E. Abdou, A. A. Mohamed, J. P. Fackler, Chem. Commun. 2003, 2882.
         | Crossref | GoogleScholarGoogle Scholar |
      (j) F. Feil, S. Harder, Eur. J. Inorg. Chem. 2005, 4438.
         | Crossref | GoogleScholarGoogle Scholar |
      (k) C. B. Wilder, L. L. Reitfort, K. A. Abboud, L. McElwee-White, Inorg. Chem. 2006, 45, 263.
         | Crossref | GoogleScholarGoogle Scholar |
      (l) D. Rische, A. Baunemann, M. Winter, R. A. Fischer, Inorg. Chem. 2006, 45, 269.
         | Crossref | GoogleScholarGoogle Scholar |
      (m) F. T. Edelmann, Chem. Soc. Rev. 2009, 38, 2253.
         | Crossref | GoogleScholarGoogle Scholar |
      (n) G. M. Chiarella, D. Y. Melgarejo, A. Rozanski, P. Hempte, L. M. Perez, C. Reber, J. P. Fackler, Chem. Commun. 2010, 46, 136.
         | Crossref | GoogleScholarGoogle Scholar |
      (o) R. Lee, Y. Y. Yang, G. K. Tan, C.-H. Tan, K.-W. Wang, Dalton Trans. 2010, 39, 723.
         | Crossref | GoogleScholarGoogle Scholar |
      (p) M. P. Coles, Chem. Commun. 2009, 3659.
         | Crossref | GoogleScholarGoogle Scholar |
      (q) C. Jones, Coord. Chem. Rev. 2010, 254, 1273.
         | Crossref | GoogleScholarGoogle Scholar |
      (r) H. Dong, Q. Meng, B.-Z. Chen, Y.-B. Wu, J. Organomet. Chem. 2012, 717, 108.
         | Crossref | GoogleScholarGoogle Scholar |
      (s) S. Collins, Coord. Chem. Rev. 2011, 255, 118.
         | Crossref | GoogleScholarGoogle Scholar |
      (t) D. Heitmann, C. Jones, D. P. Mills, A. Stasch, Dalton Trans. 2010, 39, 1877.
         | Crossref | GoogleScholarGoogle Scholar |

[2]  J. Deutsch, R. Eckelt, A. Köckritz, A. Martin, Tetrahedron 2009, 65, 10365.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsVWms7jO&md5=6616d2410605037144f0ebb8a2bbe0faCAS |

[3]  The names of the various bicyclic guanidinate precursors mentioned in this account are: Hhpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine; HTMhpp = 3,3,7,7-tetramethyl-1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine; HTEhpp = 3,3,7,7-tetraethyl-1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine; Htbo = 2,3,5,6-tetrahydro-1H-imidazo[1,2-a]imidazole; Htbn = 2,3,5,6,7,8-hexahydroimidazo[1,2-a]pyrimidine; Htbu = 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a][1,3]diazepine; Htbd = 2,5,6,7,8,9-hexahydro-3H-imidazo[1,2-a][1,3]diazepine.

[4]  F. A. Cotton, J. H. Matonic, C. A. Murillo, J. Am. Chem. Soc. 1997, 119, 7889.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXlt1yktb0%3D&md5=77400e226b4b4bbb10ec2b851a794ac1CAS |

[5]  F. A. Cotton, C. A. Murillo, X. Wang, C. C. Wilkinson, Inorg. Chim. Acta 2003, 351, 191.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXlsVCkurc%3D&md5=0167aba7bfcc0f11eae2b5674867ce82CAS |

[6]  R. Clérac, F. A. Cotton, J. P. Donahue, C. A. Murillo, D. J. Timmons, Inorg. Chem. 2000, 39, 2581.
         | Crossref | GoogleScholarGoogle Scholar | 11197013PubMed |

[7]  G. M. Chiarella, F. A. Cotton, C. A. Murillo, Chem. Commun. 2011, 47, 8940.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXpt1Kqs70%3D&md5=acc4691b187c557cd4e10bb5df2bd565CAS |

[8]  F. A. Cotton, C. A. Murillo, D. J. Timmons, Chem. Commun. 1999, 1427.
         | Crossref | GoogleScholarGoogle Scholar |

[9]  F. A. Cotton, J. Gu, C. A. Murillo, D. J. Timmons, J. Am. Chem. Soc. 1998, 120, 13280.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXns1yltr0%3D&md5=715477a1398781bd41c84d4d9fdfd80aCAS |

[10]  F. A. Cotton, N. S. Dalal, E. A. Hillard, P. Huang, C. A. Murillo, C. M. Ramsey, Inorg. Chem. 2003, 42, 1388.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXosVWguw%3D%3D&md5=ff3b5a8eb9f0463feb4d775a2e29bc5eCAS | 12611500PubMed |

[11]  F. A. Cotton, P. Huang, C. A. Murillo, D. J. Timmons, Inorg. Chem. Commun. 2002, 5, 501.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xkslars7k%3D&md5=d43bfee1c27d24d4735ca8011de6c82cCAS |

[12]  J. F. Berry, F. A. Cotton, P. Huang, C. A. Murillo, Dalton Trans. 2003, 1218.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXitlGgsLo%3D&md5=7ef1285d2f2ceb41495922f2f1b2b1ffCAS |

[13]  (a) For example, see: F. A. Cotton, N. S. Dalal, P. Huang, C. A. Murillo, A. C. Stowe, X. Wang, Inorg. Chem. 2003, 42, 670.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXitVGitQ%3D%3D&md5=1145ec7f7fa7aa125a4821cdf90ebb01CAS | 12562178PubMed |
      (b) F. A. Cotton, G. M. Chiarella, N. S. Dalal, C. A. Murillo, Z. Wang, M. D. Young, Inorg. Chem. 2010, 49, 319.
         | Crossref | GoogleScholarGoogle Scholar |

[14]  J. F. Berry, F. A. Cotton, P. Huang, C. A. Murillo, X. Wang, Dalton Trans. 2005, 3713.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXht1Sgt7bJ&md5=155c767caee27e30822e43beaf78dd79CAS | 16471049PubMed |

[15]  F. A. Cotton, J. P. Donahue, D. L. Lichtenberger, C. A. Murillo, D. Villagrán, J. Am. Chem. Soc. 2005, 127, 10808.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXmtlSnur0%3D&md5=bde7e65244e96e7e8a1e1bbb743e86bbCAS | 16076168PubMed |

[16]  Multiple Bonds Between Metal Atoms, 3rd edn (Eds F. A. Cotton, C. A. Murillo, R. A. Walton) 2005 (Springer Science and Business Media, Inc.: New York, NY).

[17]  F. A. Cotton, N. F. Curtis, C. B. Harris, B. F. G. Johnson, S. J. Lippard, J. T. Mague, W. R. Robinson, J. S. Wood, Science 1964, 145, 1305.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF2cXkvVWntbs%3D&md5=dfce950ac73edc5d6352afbffefdec79CAS | 17802015PubMed |

[18]  F. A. Cotton, L. M. Daniels, E. A. Hillard, C. A. Murillo, Inorg. Chem. 2002, 41, 2466.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XisVeju78%3D&md5=958f893464c3aab7b7129afa61bc5dfaCAS | 11978114PubMed |

[19]  F. A. Cotton, E. A. Hillard, C. A. Murillo, Inorg. Chem. 2002, 41, 1639.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XhtlCmt7Y%3D&md5=e9dac80d47e17e3790408fea9669ac3bCAS | 11896734PubMed |

[20]  F. A. Cotton, E. Pederson, Inorg. Chem. 1975, 14, 399.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2MXkvVOht7g%3D&md5=17c464a336ee5650937b90ff2e2314eeCAS |

[21]  See table 4.13 (page 138) in Ref. [16].

[22]  F. A. Cotton, L. M. Daniels, C. A. Murillo, D. J. Timmons, C. C. Wilkinson, J. Am. Chem. Soc. 2002, 124, 9249.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xlt1Gkt7c%3D&md5=05bc99cd42896154591fc13251af2a5bCAS | 12149031PubMed |

[23]  P. J. Bailey, S. F. Bone, L. A. Mitchell, S. Parsons, K. J. Taylor, L. J. Yellowlees, Inorg. Chem. 1997, 36, 867.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXhsVSksb8%3D&md5=a157c9429b6e0522156b97d71e0f8b45CAS |

[24]  F. A. Cotton, C. A. Murillo, X. Wang, C. C. Wilkinson, Inorg. Chem. 2006, 45, 5493.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XlsFOqsLs%3D&md5=edf199b393ebbac66b7589d04ada5b1fCAS | 16813412PubMed |

[25]  F. A. Cotton, C. A. Murillo, X. Wang, C. C. Wilkinson, Dalton Trans. 2006, 4623.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XhtVajsbjL&md5=36e698e3481e843e5c06031e1854ffdfCAS | 17016574PubMed |

[26]  F. A. Cotton, J. P. Donahue, N. E. Gruhn, D. L. Lichtenberger, C. A. Murillo, D. J. Timmons, L. O. Van Dorn, D. Villagrán, X. Wang, Inorg. Chem. 2006, 45, 201.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXht1OqtbrM&md5=2decdc84f0d13df66a7feb35c6c20f6eCAS | 16390057PubMed |

[27]  J. L. Robbins, N. Edelstein, B. Spencer, J. C. Smart, J. Am. Chem. Soc. 1982, 104, 1882.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL38XhsVejtL0%3D&md5=b84313a118af054d3d00a5f11d242c67CAS |

[28]  F. A. Cotton, P. Huang, C. A. Murillo, X. Wang, Inorg. Chem. Commun. 2003, 6, 121.
         | Crossref | GoogleScholarGoogle Scholar |

[29]  F. A. Cotton, N. S. Dalal, P. Huang, S. A. Ibragimov, C. A. Murillo, P. M. B. Piccoli, C. M. Ramsey, A. J. Schultz, X. Wang, Q. Zhao, Inorg. Chem. 2007, 46, 1718.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXnsVyqtA%3D%3D&md5=d3447c164f93b45ae3e08ccc68fc5c53CAS | 17243673PubMed |

[30]  G. M. Chiarella, F. A. Cotton, C. A. Murillo, M. D. Young, Inorg. Chem. 2011, 50, 1258.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXoslOqsQ%3D%3D&md5=d21fcab936b3f116d2427b2de4f79d82CAS | 21250639PubMed |

[31]  F. A. Cotton, E. A. Hillard, C. A. Murillo, Inorg. Chem. 2002, 41, 1639.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XhtlCmt7Y%3D&md5=e9dac80d47e17e3790408fea9669ac3bCAS | 11896734PubMed |

[32]  F. A. Cotton, L. M. Daniels, P. Huang, C. A. Murillo, Inorg. Chem. 2002, 41, 317.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXpt1Cgur0%3D&md5=244dab14b18b1ba8d49f6af67f8f76adCAS | 11800620PubMed |

[33]  F. A. Cotton, N. E. Gruhn, J. Gu, P. Huang, D. L. Lichtenberger, C. A. Murillo, L. O. Van Dorn, C. C. Wilkinson, Science 2002, 298, 1971.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xpt1Wis7c%3D&md5=d1307b7d8f60e542507847ccb058706fCAS | 12471252PubMed |

[34]     (a) C. E. Moore, Ionization Potentials and Ionization Limit Derived from the Analysis of Optical Spectra 1970 (NSRDSNBS 34, National Bureau of Standards, Washington, DC).
         (b) W. C. Martin, W. L. Wiese, in Atomic, Molecular & Optical Physics Handbook (Ed. G. W. F. Drake) 1996, pp. 135–153 (American Institute of Physics: Woodbury, NY).

[35]  G. M. Chiarella, F. A. Cotton, J. C. Durivage, D. L. Lichtenberger, C. A. Murillo, J. Am. Chem. Soc. 2013, 135, 17889.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhs1yls7%2FM&md5=4d7a68f94b37d727ac5417bb1d809bbcCAS | 24161128PubMed |

[36]  F. A. Cotton, J. C. Durivage, N. E. Gruhn, D. L. Lichtenberger, C. A. Murillo, L. O. Van Dorn, C. C. Wilkinson, J. Phys. Chem. B 2006, 110, 19793.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XkvVWhtro%3D&md5=a8187af5aacdafd5c90f2ce1bb5667b5CAS | 17020363PubMed |

[37]  I. Novak, X. Wei, W. S. Chin, J. Phys. Chem. A 2001, 105, 1783.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXhtVynsLc%3D&md5=7f22f5841d76bf1d74213cb8f5398378CAS |

[38]  F. A. Cotton, C. A. Murillo, X. Wang, C. C. Wilkinson, Dalton Trans. 2007, 3943.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtVOktbnN&md5=7b5d1172f8bb366ebb509bdeebff2999CAS | 17893792PubMed |

[39]  G. M. Chiarella, F. A. Cotton, S. A. Ibragimov, C. A. Murillo, C. C. Wilkinson, M. D. Young, Polyhedron 2013, 58, 7.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtVCjtL%2FO&md5=5fa0a958ba890e0a85210e2e762358a2CAS |