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(Guanidine)Copper Complexes: Structural Variety and Application in Bioinorganic Chemistry and Catalysis

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(Guanidine)Copper Complexes: Structural Variety and Application in Bioinorganic Chemistry and Catalysis Rev Inorg Chem 31 (2011): 83–108 © 2011 by Walter de Gruyter • Berlin • Boston. DOI 10.1515/REVIC.2011.003 (Guanidine)copper complexes: structural variety and application in bioinorganic chemistry and catalysis Olga Bienemann, Alexander Hoffmann and the imidazolin-2-iminato ligands which have been established Sonja Herres-Pawlis * as powerful ancillary ligands in catalysis (Kuhn et al. 1995, Anorganische Chemie II , Technische Universit ä t 1997 , Tamm et al. 2004 , 2006 , Beer et al. 2007a,b , 2008 , 2009, Dortmund, Otto-Hahn-Stra ß e 6, D-44227 Dortmund , Stelzig et al. 2008 , Haberlag et al. 2010 , Sharma et al. 2010 , Germany Trambitas et al. 2010, 2011 ). As the use of neutral guanidines emerged in coordination chemistry, they have been consid- * Corresponding author ered in reviews, but always stood in the shadow of the more e-mail: [email protected] thoroughly investigated guanidinates (Mehrota 1987 , Kuhn et al. 1995, 1997 , Mitewa 1995 , Bailey and Pace 2001 , Tamm et al. 2004, 2006 , Coles 2006 , Beer et al. 2007a,b , 2008, 2009 , Abstract Edelmann 2008 , Stelzig et al. 2008 , Haberlag et al. 2010 , Sharma et al. 2010 , Trambitas et al. 2010, 2011 ). In this paper, guanidine copper compounds are reviewed with Guanidines and guanidinates contain at least one Y-shaped an emphasis on structural characteristics and their application CN moiety which shows a special delocalisation behaviour of in bioinorganic chemistry and catalysis. The literature sur- 3 the six π -electrons which has been discussed as Y-aromaticity vey includes the copper coordination chemistry of biologi- (Gobbi and Frenking 1993 ). This resonance stabilisation is cal guanidine derivatives, peralkylated guanidines including a major reason for the high basicity of guanidines (pK of bicyclic ones and of further nitrogen-rich guanidine-type BH + [H-NMe-C(NMe ) ] in MeCN: 25.00) (Schwesinger 1990 , systems such as azoimidazoles, triazolopyrimidines and tri- 2 2 Sundermeyer et al. 2009 ). In a special case, the CN group is aminoguanidines. From a sporadic interest dating back to the 3 part of a bigger C N unit in the so-called biguanides which 1960s, research on this ligand class and its use in copper coor- 2 5 have found prominent use as an antidiabetic drug (metformin) dination chemistry has gained new impetus since 2000. With (Sch ä fer 1983 ). The chemistry of biguanides and their com- the synthesis of examples with sophisticated substitution at plexes has been reviewed elsewhere (Ray 1961 , Ray and the characteristic CN framework, complex problems can be 3 Kauffman 1999 , Hubberstey and Suksangpanya 2004 ). addressed in several fi elds of chemistry. This paper analyses the different types of guanidines for their special donor prop- In nature, organic guanidines occur ubiquitous for several erties and highlights the specifi c advantages of guanidines as reasons: (i) their facile biosynthesis starting from the amino neutral donor ligands in copper coordination chemistry where acid arginine makes this functional group relatively easily a great variety of coordination modes was found. These com- accessible; (ii) owing to their basicity, they are protonated pounds offer the ability to distribute the formal positive charge in aqueous media and act as guanidinium cations in stabilis- of the metal throughout the guanidine unit and represent more ing tertiary structures through multiple hydrogen bonds; and than simple σ -donating ligands. (iii) their donor strength enables them to coordinate to transi- tion metals. The resulting fl ourishing wealth of isolated and Keywords: azoimidazoles; copper; guanidines; chemically synthesised natural products containing guanidine imidazolin-2-imines; triazolopyrimidines. groups is regularly reviewed (Berlinck et al. 2010 ). Parallel to this biological guanidine chemistry, applica- tions as ionic liquids (Gao et al. 2005, Sauer et al. 2008 ) and Introduction in organocatalysis have emerged (Ishikawa and Kumamoto 2006 , Ishikawa 2009 , Kiesewetter et al. 2009 ). In technical The coordination chemistry of guanidines developed rather systems, guanidines are found as components or intermedi- slowly in the past decades but benefi ted from a rapid expan- ates in the production of pharmaceutics and pesticides such sion in the past 10 years. This may be due to the high basic- as chloronicotinylguanidine (Kagabu and Hirozumi Matsuno ity of the neutral guanidines and the facile formation of 1997 ). Some guanidinium salts have become important as guanidinium species upon contact with proton sources. In impregnants or fl ameproofi ng agents as well as emulsifi ers or contrast to this, the coordination chemistry of guanidinates antistatic agents in the textile industry ( G ü thner et al. 2006 ). - = 2- Copper guanidinum nitrate is used in pyrotechnic formula- [(RN)2 CNR2 ] and [(RN)2 C NR] is already known for a rich variety of coordination modes and excellent donor proper- tions (Kosanke et al. 2004 ). ties leading to compatibility with a wide range of metal ions In academia, neutral guanidines have been the focus of from all parts of the periodic table since the 1960s (Scheme considerable interest since 2000, owing to their ability to 1 ). For this reason, guanidinate chemistry has already been coordinate copper in a multitude of coordination motifs. The δ thoroughly reviewed by Bailey and Pace (2001) , Edelmann Nimine donor function resembles the -imine donor function of (2008) , and Coles (2006) . A special class of guanidinates are histidine which makes them highly valuable for the synthesis Brought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 6/2/15 7:44 PM 84 O. Bienemann et al.: (Guanidine)copper complexes R1 5 5 R R H N R N N R2 1 4 1 4 C N R R R R 3 N N N N R N R2 R3 R2 R3 4 Guanidine Guanidinium R R4 R3 R6 R7 N N N N N 1 1 2 1 4 1 R R R R R R R5 N N NN N N N N N 2 3 2 3 R R R R R2 R3 R4 Guanidinate (1-) Guanidinate (2-) Imidazolin-2-iminate Biguanide Scheme 1 Generic representations for guanidine derivates and resonance stabilisation in neutral guanidines. of bioinorganic copper complexes mimicking type 2 and type easily be changed by various methods and only a selection 3 copper proteins (Sundermeyer et al. 2009 ). of ligands is depicted in Scheme 2 (Bailey and Pace 2001 , The present review focuses on the copper coordination K ö hn et al. 2004, 2005, 2006 , Oakley et al. 2004c , Edelmann chemistry of neutral guanidines containing a substituted 2008). Without having been used until now in copper chem- = RN C(NR2 )2 moiety because the coordination chemistry of istry, the chiral pyrrolidine-1-carboximidamides should be this specifi c ligand class has been developed very successfully listed here for their good chelating properties explored in towards numerous applications in bioinorganic chemistry and zinc and molybdenum chemistry ( K ö hn et al. 2004, 2005, catalysis. The wealth of guanidine stabilised copper com- 2006 ). plexes was classifi ed into different groups depending on the The TMG unit was also successfully used by Bunge and subtype of guanidine functionality incorporated into a bigger coworkers who reported copper compounds with interesting framework. As larger sub-categories, biologically occurring polynuclear motifs containing the anionic form of TMG as guanidines, peralkylated guanidines and further nitrogen-rich guanidinate (Bunge and Steele 2009 , Bunge et al. 2009 ). guanidine-type ligands have been identifi ed. Biologically occurring guanidines Mono(guanidine) systems The most prominent naturally occurring guanidines used for The fi rst acyclic guanidine adducts were reported in 1965 copper coordination chemistry are arginine, creatinine and when Longhi and Drago presented a series of complexes of isocytosine. In nature, arginine serves as a water solubil- 1,1,3,3-tetramethylguanidine (TMG) at divalent transition ity mediating functional group or as a carboxylate-specifi c metals (Longhi and Drago 1965 ). In the following decades, hydrogen bond donor in proteins and other natural products. the coordination chemistry much preferred the anionic forms The challenge in using these compounds for coordination of guanidines (Kuhn et al. 1995, 1997 , Bailey and Pace 2001 , chemistry lies in the potential choice of the binding site for Tamm et al. 2004, 2006, Coles 2006 , Beer et al. 2007a,b , the metal and multiple tautomeric forms (Scheme 3 ). For 2008 , Edelmann 2008, Stelzig et al. 2008 , Haberlag et al. example, the search for tautomers and conformers of the 2010 , Sharma et al. 2010 , Trambitas et al. 2010, 2011 ). In small molecule arginine is still a vital fi eld of recent research the 1990s, Schneider et al. used TMG as ancillary ligands for (Di Costanzo et al. 2006 , Schlund et al. 2008 ). Understanding the stabilisation of gold complexes (Schneider et al. 1997 ), the role of copper in DNA binding is crucial as Cu(II) medi- but the use for copper chemistry remained underdeveloped. ates polypeptide-polynucleotide interactions (Bean et al. Only in 2004, Coles et al. reported a binuclear copper iodido 1977 , Koren and Mildvan 1977 , Bere and Helene 1979 ). complex with two molecules of Me2 NC(N i Pr)(NH i Pr) and Additionally, copper supports self-assembly processes but no hydrogen bonding was observed in the solid state (Oakley also radical processes involving hydroxyl radicals (Minisci et al. 2004c ). The substitution pattern of the CN 3 unit can 1996 , Leininger et al. 2000 , Swiegers and Malefetse 2000 ). NH NiPrR NiPr R=1-pyrrolidinyl 4-morpholinyl i i 1-piperidinyl Me2N NMe2 Me2N NH PrN NH Pr i i TMG Me2NC(N Pr)(NH Pr) Pyrrolidine-1-carboximidamides Scheme 2 Examples of mono(guanidine) ligands used in coordination chemistry. Brought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 6/2/15 7:44 PM O. Bienemann et al.: (Guanidine)copper complexes 85 NH2 2000, 2001 ).
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