Two dinuclear Cu II complexes based on a diazecine ligand were characterized by X-ray diffraction, one of which includes the rare Cu II–F bond, resulting from dissociation of a BF 4 ? ion. The F ? ligands actively participate in the crystal structure, behaving as acceptors for hydrogen bonding.
References
[1]
Although following the IUPAC rules the coordinated F? anion should be named “fluorido”, we prefer to follow the common practice of naming this ligand “fluoride” throughout this paper.
[2]
Conner, M.; McConnell, A.; Schlueter, J.; Manson, J. Structural and magnetic properties of copper(II) coordination polymers containing fluoride-based anions and ancillary organic ligands. J. Low Temp. Phys. 2006, 142, 273–278, doi:10.1007/BF02679507.
[3]
Manson, J.L.; Schlueter, J.A.; Funk, K.A.; Southerland, H.I.; Twamley, B.; Lancaster, T.; Blundell, S.J.; Baker, P.J.; Pratt, F.L.; Singleton, J.; et al. Strong H···F hydrogen bonds as synthons in polymeric quantum magnets: Structural, magnetic, and theoretical characterization of [Cu(HF2)(pyrazine)2]SbF6, [Cu2F(HF)(HF2)(pyrazine)4](SbF6)2, and [CuAg(H3F4)(pyrazine)5](SbF6)2. J. Am. Chem. Soc. 2009, 131, 6733–6747.
[4]
Emsley, J.; Reza, N.M.; Dawes, H.M.; Hursthouse, M.B. Diaquadifluorobis(nicotinamide) copper(II) tetrahydrate: Hydrogen bonding between ligand fluoride and lattice water. J. Chem. Soc. Dalton Trans. 1986, 313–316.
[5]
Emsley, J.; Arif, M.; Bates, P.A.; Hursthouse, M.B. Aqua(2,2'-bipyridyl)difluorocopper(II) dihydrate: X-ray structure reveals short hydrogen bonds and other unusual features. J. Chem. Soc. Dalton Trans. 1987, 2397–2399.
[6]
Mokuolu, Q.F.; Foguet-Albiol, D.; Jones, L.F.; Wolowska, J.; Kowalczyk, R.M.; Kilner, C.A.; Christou, G.; McGowan, P.C.; Halcrow, M.A. Four copper(II) pyrazolido complexes derived from reactions of 3{5}-substituted pyrazoles with CuF2 or Cu(OH)2. Dalton Trans. 2007, 1392–1399.
[7]
Guichelaar, M.A.; Van Hest, J.A.M.; Reedijk, J. Formation of solid fluoride complexes from metal(II) tetrafluoroborates. Inorg. Nucl. Chem. Lett. 1974, 10, 999–1004, doi:10.1016/0020-1650(74)80027-9.
[8]
Van Rijn, J.; Reedijk, J.; Dartmann, M.; Krebs, B. Copper(I) and copper(II) compounds of a dinucleating, octadentate tetrakisbenzimidazole ligand. Crystal and molecular structures of three dihalogeno{1,8-bis[bis(1'-methylbenzimidazol-2'-ylmethyl)amino]-3,6-dioxaoctane}dicopper(II) bis(anion) compounds (halogen = F, Cl, or Br; anion = BF4, CF3SO3, or Cl). J. Chem. Soc. Dalton Trans. 1987, 2579–2593.
[9]
Van Albada, G.A.; Roubeau, O.; Mutikainen, I.; Turpeinen, U.; Reedijk, J. A unique methoxo- and fluoro-bridged triangular trinuclear Cu(II) species linked in a lattice via mononuclear Cu(II) units. Synthesis, X-ray structure and magnetism of [Cu4(2-aminopyrimidine)6(μ3-OCH3)2(μ-F)3(F)2](BF4). New J. Chem. 2003, 27, 1693–1697, doi:10.1039/b304979e.
[10]
Casellas, H.; Pevec, A.; Kozlev?ar, B.; Gamez, P.; Reedijk, J. An unprecedented μ4-SiF62?-bridged supramolecular polymer consisting of bis-μ-F? bridged dinuclear Cu(II) dications. Polyhedron 2005, 24, 1549–1554, doi:10.1016/j.poly.2005.04.011.
[11]
Keij, F.S.; De Graaff, R.A.G.; Haasnoot, J.G.; Oosterling, A.J.; Pedersen, E.; Reedijk, J. The first difluoro-bridged copper chain, and alternating zig-zag, stabilized by a unique intrachain hydrogen bond system. Crystal and molecular structure of Catena-poly[di-μ-fluoro-bis(3-methyl-4-ethyl-5-phenylpyrazole)copper(II)]. J. Chem. Soc. Chem. Commun. 1988, 423–425.
[12]
Keij, F.S.; De Graaff, R.A.G.; Haasnoot, J.G.; Reedijk, J.; Pedersen, E. An unusual hexafluorosilicato-bridged chain compound; crystal structure of catena-(μ-Hexafluorosilicato)-tetrakis(5-phenylpyrazole)copper(II). Inorg. Chim. Acta 1989, 156, 65–70, doi:10.1016/S0020-1693(00)90369-4.
[13]
Oosterling, A.J.; De Graaff, R.A.G.; Haasnoot, J.G.; Keij, F.S.; Reedijk, J.; Pedersen, E. Spectroscopic and magnetic identification of difluoro-bridged zigzag copper chains with substituted 5-phenylpyrazole ligands. Structural identification of catena-poly [bis(3-methyl-4-ethyl-5-phenylpyrazole)copper-di-μ-fluoro]. Inorg. Chim. Acta 1989, 163, 53–58, doi:10.1016/S0020-1693(00)87141-8.
[14]
Almes?ker, A.; Gamez, P.; Reedijk, J.; Scott, J.L.; Spiccia, L.; Teat, S.J. Stabilisation of a very short Cu-F bond within the protected cavity of a copper(II) compound from a tris(2-aminoethyl)amine derivative. Dalton Trans. 2009, 4077–4080.
[15]
Barlow, S.J.; Hill, S.J.; Hocking, J.E.; Hubberstey, P.; Li, W.-S. Crystal and molecular structure of [{Cu(pmdien)F(H2O)}2][BF4]2 (pmdien = N,N,N′,N″,N″-pentamethyldiethylenetriamine): A novel dimeric cation with extremely short O-H···F interactions. J. Chem. Soc. Dalton Trans. 1997, 4701–4704.
[16]
Ackermann, J.; Meyer, F.; Pritzkow, H. Compartmental pyrazolate ligands providing two adjacent tris(pyridylalkyl)amine-type binding pockets and their dicopper(II) fluoride complexes featuring extremely short intramolecular O-H···F bridges. Inorg. Chim. Acta 2004, 357, 3703–3711, doi:10.1016/j.ica.2004.04.023.
[17]
Tomat, E.; Cuesta, L.; Lynch, V.M.; Sessler, J.L. Binuclear fluoro-bridged zinc and cadmium complexes of a Schiff base expanded porphyrin: Fluoride abstraction from the tetrafluoroborate anion. Inorg. Chem. 2007, 46, 6224–6226, doi:10.1021/ic700933p.
Min, K.S.; Arif, A.M.; Miller, J.S. Synthesis, structure and magnetic properties of an oxo-bridged dinuclear iron(III) complex [(TPyA)FFeIIIOFeIIIF(TPyA)](BF4)2·0.5MeOH (TPyA = tris(2-pyridylmethyl)amine) containing the FFeIIIOFeIIIF linkage. Inorg. Chim. Acta 2007, 360, 1854–1858, doi:10.1016/j.ica.2006.09.020.
[20]
Reedijk, J. Formation of fluoride-containing coordination compounds by decomposition of transition-metal tetrafluoroborates. Comments Inorg. Chem. 1982, 1, 379–389, doi:10.1080/02603598208078105.
[21]
Reedijk, J.; Jansen, J.C.; Van Koningsveld, H.; Van Kralingen, C.G. Synthesis, structure, and spectroscopic and magnetic properties of a new class of dimeric, fluoro-bridged high-spin cobalt(II) compounds containing substituted-pyrazole ligands. Inorg. Chem. 1978, 17, 1990–1994, doi:10.1021/ic50185a060.
[22]
Manzur, J.; Vega, A.; García, A.M.; Acu?a, C.; Sieger, M.; Sarkar, B.; Niemeyer, M.; Lissner, F.; Schleid, T.; Kaim, W. Coordination Alternatives In Dinuclear Bis(Pyridin-2-Ylalkyl)Benzylaminecopper(II) Complexes With OH-, RO-, F-, Or Cl- Bridges: Experimental Structures And DFT preferences. Eur. J. Inorg. Chem. 2007, 5500–5510.
[23]
Straub, B.F.; Rominger, F.; Hofmann, P. A trigonal planar μ3-fluorido coinage metal complex from a dicationic (diphosphinomethane)copper(I) dimer: syntheses, structures, and bonding. Inorg. Chem. 2000, 39, 2113–2119, doi:10.1021/ic991173w.
[24]
Schatz, M.; Becker, M.; Thaler, F.; Hampel, F.; Schindler, S.; Jacobson, R.R.; Tyeklár, Z.; Murthy, N.N.; Ghosh, P.; Chen, Q.; Zubieta, J.; Karlin, K.D. Copper(I) complexes, copper(I)/O2 reactivity, and copper(II) complex adducts, with a series of tetradentate tripyridylalkylamine tripodal ligands. Inorg. Chem. 2001, 40, 2312–2322.
[25]
Jacobson, R.R.; Tyeklár, Z.; Karlin, K.D.; Zubieta, J. Fluoride as a terminal and bridging ligand for copper: Isolation and X-ray crystallographic characterization of copper monomeric and dimeric complexes [CuII(TMPA)F]nn+ (n = 1 or 2; TMPA = tris[(2-pyridyl)methyl]amine). Inorg. Chem. 1991, 30, 2035–2040, doi:10.1021/ic00009a017.
Gasque, L.; Mijangos, E.; Ortiz-Frade, L. [μ-5,11-Bis(dimethylethyleneamino)-2,8-dimethyl-1,4,5,6,7,10,11,12-octahydroimidazo[4,5-h]imidazo[4,5-c][1,6]diazecine]bis[aquasulfatocopper(II)] hexahydrate: A dinuclear copper sulfate complex based on a diazecine ligand. Acta Crystallogr. 2005, E61, m673–m676.
[28]
Gasque, L.; Ugalde-Saldívar, V.M.; Membrillo, I.; Olguín, J.; Mijangos, E.; Bernès, S.; González, I. A dicopper complex with distant metal centers. Structure, magnetic properties, electrochemistry and catecholase activity. J. Inorg. Biochem. 2008, 102, 1227–1235, doi:10.1016/j.jinorgbio.2007.12.032.
[29]
Driessen, W.L.; Rehorst, D.; Reedijk, J.; Mutikainen, I.; Turpeinen, U. Copper(II) compounds of some rigid dinucleating bis-amine-bis-imidazole ligands. Inorg. Chim. Acta 2005, 358, 2167–2173, doi:10.1016/j.ica.2004.03.062.
[30]
Mautner, F.A.; Grebowicz, J.; Deifik, P.J.; Perkins, R.S.; Massoud, S.S. Structural characterization of copper(II) complexes based on a new 10-membered binucleating 1,6-diazecine ligand. J. Mol. Struct. 2009, 933, 69–76, doi:10.1016/j.molstruc.2009.05.059.
[31]
Etter, M.C. Encoding and decoding hydrogen-bond patterns of organic compounds. Acc. Chem. Res. 1990, 23, 120–126, doi:10.1021/ar00172a005.
[32]
Borrás, J.; Alzuet, G.; González-Alvarez, M.; García-Giménez, J.L.; Macías, B.; Liu-González, M. Efficient DNA cleavage induced by copper(II) complexes of hydrolysis derivatives of 2,4,6-Tri(2-pyridyl)-1,3,5-triazine in the presence of reducing agents. Eur. J. Inorg. Chem. 2007, 822–834.