Register      Login
Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH FRONT

New Square-Planar Bis(Dithiolene) Complexes: Synthesis, Crystallography, and Properties of [Bu4N][MIII(btdt)2] (M = Cu, Au) and [Bu4N]2[PtII(btdt)2] ({btdt}2– =2,1,3-Benzenethiadiazole-5,6-dithiolate)

Ramababu Bolligarla A and Samar K. Das A B
+ Author Affiliations
- Author Affiliations

A School of Chemistry, University of Hyderabad, Hyderabad 500 046, India.

B Corresponding author. Email: skdsc@uohyd.ernet.in

Australian Journal of Chemistry 64(5) 550-560 https://doi.org/10.1071/CH11075
Submitted: 15 February 2011  Accepted: 9 March 2011   Published: 30 May 2011

Abstract

The syntheses, crystal structures, and properties of three new coordination complexes [Bu4N][MIII(btdt)2] [M = Cu (1), Au (2)] and [Bu4N]2[PtII(btdt)2] (3) ({btdt}2– = 2,1,3-benzenethiadiazole-5,6-dithiolate) are described. Compounds 13 crystallize in a triclinic P-1, and monoclinic P2(1)/c and C2/c space groups, respectively. The {MS4} chromophore lies in almost a square-planar coordination environment in complex 1, but has a slightly distorted square-planar geometry around the central metal ion in compounds 2 and 3. Interactions in the solid state have been studied by intermolecular contacts, in particular, compounds 2 and 3 have been characterized by SN and SS non-covalent interactions among dithiolate complexes, resulting in two- and one-dimensional supramolecular motifs, respectively. Complexes 13 show broad absorption bands in the visible region, with that of 3 being sensitive to solvent polarity. Complex 1 exhibits a very low reduction potential for a CuIII-coordination complex, while the PtII complex 3 shows two irreversible oxidative responses at 0.45 V and 0.74 V versus Ag/AgCl, respectively.


References

[1]  K. D. Karlin, E. I. Stiefel (Eds), Progress in Inorganic Chemistry 2004, Vol. 52 (John Wiley: New York, NY).

[2]  R. Kato, Chem. Rev. 2004, 104, 5319.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXntVCktr0%3D&md5=37d6bb00495fd5a626a1de40be29a9ffCAS | 15535652PubMed |

[3]  M. L. Mercuri, P. Deplano, L. Pilia, A. Serpe, F. Artizzu, Coord. Chem. Rev. 2010, 254, 1419.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXlsVGjtrw%3D&md5=d72401b26d9c9c8714b39a8665a2bc10CAS |

[4]  A. T. Coomber, D. Beljonne, R. H. Friend, J. L. Brédas, A. Charlton, N. Robertson, A. E. Underhill, M. Kurmoo, P. Day, Nature 1996, 380, 144.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28Xhs1Gns7g%3D&md5=e727119df4dd931485e5be6ec684b877CAS |

[5]  X. M. Ren, S. Nishihara, T. Akutagawa, S. Noro, T. Nakamura, Inorg. Chem. 2006, 45, 2229.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XpsVGhug%3D%3D&md5=f74529ebfc203012a3cf28b4861e0bbfCAS | 16499388PubMed |

[6]  N. Robertson, L. Cronin, Coord. Chem. Rev. 2002, 227, 93.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XhslSqsLk%3D&md5=fef683131949622691935136dc0416e4CAS |

[7]  P. Deplano, L. Pilia, D. Espa, M. L. Mercuri, A. Serpe, Coord. Chem. Rev. 2010, 254, 1434.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXlsVGjtr0%3D&md5=4a64b8c8a033fe2f871cdf8c7dcb903eCAS |

[8]  L. Serrano-Andrés, A. Avramopoulos, J. Li, P. Labéguerie, D. Bégué, V. Kellö, M. G. Papadopoulos, J. Chem. Phys. 2009, 131, 134312.
         | Crossref | GoogleScholarGoogle Scholar | 19814558PubMed |

[9]  C.-T. Chen, S.-Y. Liao, K.-J. Lin, L.-L. Lai, Adv. Mater. 1998, 10, 334.
         | Crossref | GoogleScholarGoogle Scholar |

[10]  U. T. Mueller-Westerhoff, B. Vance, D. I. Yoon, Tetrahedron 1991, 47, 909.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXht1Cmtro%3D&md5=5042d822f47980656a24783eb9866d01CAS |

[11]  P. Deplano, M. L. Mercuri, G. Pintus, E. F. Trogu, Comments Inorg. Chem. 2001, 22, 353.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXns1Wrsbs%3D&md5=38cb758cac3125d519db0b0cb659c382CAS |

[12]  J.-F. Bai, J.-L. Zuo, W.-L. Tan, W. Ji, Z. Shen, H.-K. Fun, K. Chinnakali, I. A. Razak, X.-Z. You, C.-M. Che, J. Mater. Chem. 1999, 9, 2419.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXmsVGms7g%3D&md5=1fcffb60e6b44164def4a77a3016a601CAS |

[13]  M. C. Aragoni, M. Arca, T. Cassano, C. Denotti, F. A. Devillanova, R. Frau, F. Isaia, F. Lelj, V. Lippolis, L. Nitti, P. Romaniello, R. Tommasi, G. Verani, Eur. J. Inorg. Chem. 2003, 1939.
         | 1:CAS:528:DC%2BD3sXksVKnurY%3D&md5=4cb4b74fdd05eb500a86cffddb868156CAS |

[14]  F. J. Hine, A. J. Taylor, C. D. Garner, Coord. Chem. Rev. 2010, 254, 1570.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXlsVGjt7o%3D&md5=3e14ddb4188028ab2f5ed649ecf4b0e5CAS |

[15]  D. C. Rees, Y. Hu, C. Kisker, H. Sahindelin, J. Chem. Soc., Dalton Trans. 1997, 3909.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXntlOmtL0%3D&md5=e5d3d1ed53e1733a115f9ac634beee8eCAS |

[16]  M. J. Rudolph, M. M. Wuebbens, K. V. Rajagopalan, H. Sahindelin, Nat. Struct. Biol. 2001, 8, 42.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXjslyrsQ%3D%3D&md5=207bf71854dfb7698cc55831886fca89CAS | 11135669PubMed |

[17]  J. L. Johnson, K. V. Rajagopalan, Proc. Natl. Acad. Sci. USA 1982, 79, 6856.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3sXhtlGqsA%3D%3D&md5=c74aae9f78bf5c0f11156d9d9b9e72b7CAS |

[18]  J. L. Johnson, B. E. Hainline, K. V. Rajagopalan, B. H. Arison, J. Biol. Chem. 1984, 259, 5414.
         | 1:CAS:528:DyaL2cXktF2ltr4%3D&md5=0c644347408bfd608adb9eea53c4d356CAS | 6546929PubMed |

[19]  S. Boyde, C. D. Garner, J. H. Enemark, M. A. Bruck, J. G. Kristofzski, J. Chem. Soc., Dalton Trans. 1987, 2267.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXhsFWksw%3D%3D&md5=591b1ca1f18c6ce3054766a578064690CAS |

[20]  S. Boyde, C. D. Garner, J. H. Enemark, R. B. Ortega, J. Chem. Soc., Dalton Trans. 1987, 297.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2sXhtFamur8%3D&md5=ba844e2eeb4312b1f1c761a695167c14CAS |

[21]  S. Boyde, C. D. Garner, J. H. Enemark, R. B. Ortega, Polyhedron 1986, 5, 377.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL28XkvFSjt70%3D&md5=970ce2942ce9ffbb9422a3016ff160eeCAS |

[22]  A. Rignedoli, G. Peyronel, W. Malavasi, J. Inorg. Nucl. Chem. 1976, 38, 1963.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2sXot12gug%3D%3D&md5=63440d0859e48c75f270fcd9cf232b6bCAS |

[23]  L. J. Theriot, K. K. Ganguli, S. Kavarnos, I. Bernal, J. Inorg. Nucl. Chem. 1969, 31, 3133.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF1MXltFarurY%3D&md5=d79789ee21643f2bb54f11d498eeae49CAS |

[24]  S. Boyde, C. D. Garner, J. Chem. Soc., Dalton Trans. 1991, 713.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXktlOgsbk%3D&md5=e2757527d1fa2c65eee147cf1328ac26CAS |

[25]  R. W. Burke, E. R. Deardorff, Talanta 1970, 17, 255.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE3cXktFSgtbs%3D&md5=b3e27214b7459b1e5bc6a924667691d7CAS | 18960730PubMed |

[26]  O. P. Ryabushko, A. T. Pilipenko, L. A. Batkovskaya, Y. S. Savin, Ukr. Khim. Zh. 1988, 54, 1172.
         | 1:CAS:528:DyaL1MXmtVyhs7c%3D&md5=1226c65fba84f5e6e391f6f6b6a2e2b9CAS |

[27]  S. D. Cummings, R. Eisenberg, Inorg. Chem. 1995, 34, 2007.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXkvVWrs78%3D&md5=0b0f089bd530a645d13e7641495efdb1CAS |

[28]  S. D. Cummings, R. Eisenberg, Inorg. Chem. 1995, 34, 3396.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXmtVyisLg%3D&md5=7ab2678e19bf54b5538f07e054d434f9CAS |

[29]  R. Bolligarla, R. Kishore, G. Durgaprasad, S. K. Das, Inorg. Chim. Acta 2010, 363, 3061.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXht1emtLvK&md5=9db85c755defcb993f11492098702d65CAS |

[30]  J.-J. Wang, S. Groysman, S. C. Lee, R. H. Holm, J. Am. Chem. Soc. 2007, 129, 7512.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXlvVels7Y%3D&md5=b8e36f738b099c758fdc8eb3e12510bdCAS | 17530853PubMed |

[31]  K. Mrkvová, J. Kameníček, Z. Šindelář, L. Kvítek, Transition. Met. Chem. 2004, 29, 238.
         | Crossref | GoogleScholarGoogle Scholar |

[32]  J. Walla, Z. Smékal, J. Kameníček, Acta Univ. Palacki. Olom. 1998, 37.

[33]  N. C. Schiødt, T. Bjørnholm, K. Bechgaard, J. J. Neumeier, C. Allgeier, C. S. Jacobsen, N. Thorup, Phys. Rev. B 1996, 53, 1773.
         | Crossref | GoogleScholarGoogle Scholar |

[34]  N. C. Schiødt, P. Sommer-Larsen, T. Bjørnholm, M. F. Nielsen, J. Larsen, K. Bechgaard, Inorg. Chem. 1995, 34, 3688.
         | Crossref | GoogleScholarGoogle Scholar |

[35]  V. Madhu, S. K. Das, Inorg. Chem. 2008, 47, 5055.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXlvVymsbk%3D&md5=d4402ce2d5f9232b73531f6160dcb65eCAS | 18479121PubMed |

[36]  R. Bolligarla, G. Durgaprasad, S. K. Das, Inorg. Chem. Commun. 2009, 12, 355.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXltlOjsbs%3D&md5=adb96f8ef16835eeccc37a6341deae37CAS |

[37]  R. Bolligarla, G. Durgaprasad, S. K. Das, Inorg. Chem. Commun. 2011, 14.
         | Crossref | GoogleScholarGoogle Scholar |

[38]  R. Bolligarla, S. K. Das, Cryst. Eng. Commun. 2010, 12, 3409.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsVGht7jE&md5=b19899dad3b3f93729e09671ebaab01cCAS |

[39]  X. Ribas, J. Dias, J. Morgado, K. Wurst, M. Almeida, J. Veciana, C. Rovira, Cryst. Eng. Commun. 2002, 4, 564.
         | Crossref | GoogleScholarGoogle Scholar |

[40]  V. Madhu, S. K. Das, Inorg. Chem. 2006, 45, 10037.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XhtFOmtLvF&md5=fb668afa1e7a0e0f52ccca4803e12a0cCAS | 17140204PubMed |

[41]  S. I. Shupack, E. Billig, R. J. H. Clark, R. Williams, H. B. Gray, J. Am. Chem. Soc. 1964, 86, 4594.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF2cXkvV2htL0%3D&md5=4c8c76ea34cff56cad2a9cdfd0ca37c2CAS |

[42]  G. C. Papavassiliou, A. M. Cotsilios, C. S. Jacabsen, J. Mol. Struct. 1984, 115, 41.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2cXhvVanu70%3D&md5=92ed0f6fab1fe20379aa7fa028e5fba0CAS |

[43]  A. Bondi, J. Phys. Chem. 1964, 68, 441.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF2cXls1Cgsg%3D%3D&md5=3bd1fefd910662044bf9e85065a58830CAS |

[44]  J. L. Brusso, O. P. Clements, R. C. Haddon, M. E. Itkis, A. A. Leitch, R. T. Oakley, R. W. Reed, J. F. Richardson, J. Am. Chem. Soc. 2004, 126, 8256.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXksl2rt7s%3D&md5=287b5ea834cb9c80ca4badd492f44af8CAS | 15225068PubMed |

[45]  SADABS, SMART, SAINT, and SHELXTL 2000 (Bruker AXS Inc.: Madison, WI).

[46]  G. M. Sheldrick, Acta Crystallogr. A 2008, 64, 112.
         | Crossref | GoogleScholarGoogle Scholar | 18156677PubMed |