Inorg. Chem. 2004, 43, 5168−5172
Structural Consequences of the Prohibition of Hydrogen Bonding in Copper−Guanidine Systems Sarah H. Oakley, Martyn P. Coles,* and Peter B. Hitchcock Department of Chemistry, UniVersity of Sussex, Falmer, Brighton BN1 9QJ, U.K. Received March 26, 2004
The synthesis and structure of copper(I) complexes supported by N-substituted bicyclic guanidines is described. The N-methyl-substituted bicyclic guanidine 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine (hppMe) reacted with copper(I) chloride to afford the ion-pair [Cu(hppMe)2][CuCl2] (1), a rare example of a compound containing an unsupported Cu‚‚‚Cu interaction. The analogous reaction with CuI, however, afforded the molecular µ,µ-dihalobridged dimer [CuI(hppMe)]2 (2). Inclusion of a trimethylsilyl substituent at nitrogen provided a sufficiently sterically encumbered environment to support a two coordinate copper center in CuCl(hppSiMe3) (3). Compounds 1−3 have been fully characterized, including single-crystal X-ray diffraction studies.
Introduction Copper is the key element in a number of biological transformations involving small molecules mediated by metalloenzymes.1 Molecular systems which mimic the interactions of the protein with the copper atom are important in understanding such processes, and on a fundamental level, the way in which ligands containing component functionalities from proteins bind to copper will allow a more complete picture to be developed. The amino acid arginine (Arg), which contains a guanidine functionality, has been shown to interact with copper ions via both the amine nitrogen and oxygen atom of the carboxylate group, in addition to forming both intra- and intermolecular hydrogen bonds.2 These secondary H-bonding interactions have proved to be important in the self-organization of supramolecular assemblies, where, for example, the chirality of the arginine determines the “handedness” of the helicity in double helical structures formed by [Cu(Arg)2]2+ systems.3 We have recently exploited the neutral, bicyclic guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH) as a ligand in copper(I) cyano4 and halide5,6 complexes. The * Author to whom correspondence should be addressed. E-mail:
[email protected]. Tel.: +44 (0)1273 877339. Fax: +44 (0)1273 677196. (1) Stack, T. D. P. Dalton Trans. 2003, 1881. Richards, R. L.; Durrant, M. C. J. Chem. Res., Synop. 2002, 95. (2) Ohata, N.; Masuda, H.; Yamauchi, O. Inorg. Chim. Acta 2000, 300, 749; de Farias, R. F.; Martı´nez, L.; Airoldi, C. Transition Met. Chem. 2002, 27, 253. (3) Ohata, N.; Masuda, H.; Yamauchi, O. Angew. Chem., Int. Ed. Engl. 1996, 35, 531. (4) Coles, M. P.; Hitchcock, P. B. Polyhedron 2001, 20, 3027.
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molecular structures of CuCl(hppH)2 (I) and CuCl(hppH)(PPh3) (II) revealed monomeric, three-coordinate metals with intramolecular NH‚‚‚Cl hydrogen bonds. The guanidine ligands in I and II were shown, by variable-temperature NMR spectroscopy, to be fluxional in solution, with ∆Gq values lower than in Cu(I) bipy and pyridine imine complexes,7 rationalized by the formation of stable, fivemembered metallacycles with these chelating ligands. To establish the importance of such secondary interactions in Cu(I) compounds with “hpp”-based ligands, we have designed two systems which remove the NH functionality (thus negating the opportunity of NH‚‚‚X interactions) while retaining the Nimine group. First, carbon8 and silicon9 linked poly(guanidyl) ligands have been developed, where additional stability is predicted as a consequence of the chelate effect. We have shown accordingly that bis(guanidyl)methane and -silane compounds, H2C{hpp}2 and Me2Si{hpp}2, chelate to copper(I) halides affording monomeric, three-coordinate complexes. Alternatively, the coordination chemistry of N-substituted guanidines, hppX (X ) SiMe3, Me), has been examined, where more complicated situations have been observed, (5) Oakley, S. H.; Coles, M. P.; Hitchcock, P. B. Inorg. Chem. 2003, 42, 3154. (6) Oakley, S. H.; Soria, D. B.; Coles, M. P.; Hitchcock, P. B. Dalton Trans. 2004, 537. (7) Desvergnes-Breuil, V.; Hebbe, V.; Dietrich-Buchecker, C.; Sauvage, J.-P.; Lacour, J. Inorg. Chem. 2003, 42, 255. (8) Oakley, S. H.; Coles, M. P.; Hitchcock, P. B. Inorg. Chem. 2004, submitted for publication. (9) Oakley, S. H.; Coles, M. P.; Hitchcock, P. B. Dalton Trans. 2004, 1113.
10.1021/ic0495970 CCC: $27.50
© 2004 American Chemical Society Published on Web 07/13/2004
N-Substituted Guanidine Compounds of Copper(I) Table 1. Crystal Structure and Refinement Data for 1-3
formula fw temp (K) wavelength (Å) cryst system space group a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg) V (Å3) Z Dcalc (Mg/m3) abs coeff (mm-1) θ range for data collcn (deg) reflcns collcd indepndnt reflcns reflcns with I > 2σ(I) data/restraints/params goodness-of-fit on F2 final R indices [I > 2σ(I)] R indices (all data) largest diff peak and hole (e Å-3)
1
2
3
C16H30Cl2Cu2N6 504.44 173(2) 0.710 73 orthorhombic Aba2 (No. 41) 16.8277(4) 12.2576(3) 9.7062(2) 90 90 90 2002.07(8) 4 1.67 2.41 4.11-27.89 9022 2064 (Rint ) 0.042) 1943 2064/1/180 0.955 R1 ) 0.024, wR2 ) 0.054 R1 ) 0.027, wR2 ) 0.056 0.362 and -0.419
C16H30Cu2I2N6 687.34 173(2) 0.710 73 orthorhombic Pbca (No. 61) 9.5104(2) 15.1205(3) 15.3723(3) 90 90 90 2210.57(8) 4 2.07 4.73 3.78-25.04 21 411 1943 (Rint ) 0.052) 1708 1943/1/145 1.084 R1 ) 0.037, wR2 ) 0.096 R1 ) 0.045, wR2 ) 0.101 1.12 and -1.34
C10H21ClCuN3Si 310.38 173(2) 0.710 73 triclinic P1h (No. 2) 7.8072(3) 9.6668(3) 10.7091(5) 111.982(3) 97.576(3) 106.227(2) 693.77(5) 2 1.49 1.83 3.84-25.02 5274 2349 (Rint ) 0.043) 2071 2349/0/229 1.039 R1 ) 0.032, wR2 ) 0.064 R1 ) 0.039, wR2 ) 0.067 0.30 and -0.29
dependent on both the nature of the nitrogen substituent and the copper(I) halide that is employed as the starting reagent. Experimental Section General Experimental Procedures. All manipulations were carried out under dry nitrogen using standard Schlenk and cannula techniques or in a conventional nitrogen-filled glovebox operating at
