Synthesis and properties of guanidine-pyridine hybridligands and structural characterisation of their mono- and bis(chelated) cobalt complexes

Abstract The synthesis of four guanidine-pyridine hybridligands and their spectroscopic features in MeCN are described. In order to demonstrate their coordinating properties, the corresponding cobalt(II)chloride complexes have been prepared and completely characterised by means of X-ray structure analysis, UV/Vis spectroscopy and mass spectrometry. The neutral complexes {1,1,3,3-tetramethyl-2-(quinolin-8-yl)guanidine}cobalt(II)-dichloride [Co(TMGqu)Cl 2 ] and { N -(1,3-dimethylimidazolidin-2-yliden)pyridin-8-amine}cobalt(II)-dichloride [Co(DMEGpy)Cl 2 ] exhibit a tetrahedral coordination of the cobalt atom, whereas in bis[chlorobis{ N -(1,3-dimethylimidazolidin-2-yliden)quinolin-8-amine}cobalt(II)]tetrachlorocobaltate [Co(DMEGqu) 2 Cl] 2 [CoCl 4 ] and chlorobis{1,1,3,3-tetramethyl-2-((pyridin-2-yl)methyl)guanidine}cobalt(II)chloride [Co(TMGpy) 2 Cl]Cl, the cobalt atom is coordinated in a trigonal pyramidal environment. These trigonal pyramidal complex cations represent the first bis(chelated) guanidine cobalt complexes in which the pyridine donor resides on the apical position and the guanidine donor forms with the chlorine atom the base of the pyramid. Besides the structural characterisation, the quenching effect of the cobalt(II) ion ( d 7 ) on the ligand fluorescence has been studied.

[1]  A. Mangia,et al.  Spectral and magnetic properties and crystal structure of dichloro{N-[methoxy(6-methyl-2-pyridyl)methyl]benzothiazolin-2-ylideneimine}-cobalt(II) , 1972 .

[2]  Terence E. Rice,et al.  Signaling Recognition Events with Fluorescent Sensors and Switches. , 1997, Chemical reviews.

[3]  P. D. Newman,et al.  Trispyrazolylmethane piano stool complexes of iron(II) and cobalt(II) , 2006 .

[4]  T. Maier,et al.  Orthoamide. XL: Herstellung von 1,1,2,3,3-pentasubstituierten und 1,1,2,2,3,3-hexasubstituierten Guanidiniumsalzen sowie von 1,1,2,3,3-Pentaalkylguanidinen , 1984 .

[5]  O. Walter,et al.  Transformation of nitrile to cyanide and aldehyde using a cobalt(II) complex and dioxygen. , 2007, Angewandte Chemie.

[6]  Sonja Herres-Pawlis,et al.  Tuning of Copper(I)–Dioxygen Reactivity by Bis(guanidine) Ligands , 2005 .

[7]  M. P. Coles,et al.  Application of neutral amidines and guanidines in coordination chemistry. , 2006, Dalton transactions.

[8]  O. Walter,et al.  Umwandlung eines Nitrils in Cyanid und Aldehyd unter Verwendung von Sauerstoff und einem Cobalt(II)‐Komplex , 2007 .

[9]  I. Sazanovich,et al.  Structural control of the excited-state dynamics of bis(dipyrrinato)zinc complexes: self-assembling chromophores for light-harvesting architectures. , 2004, Journal of the American Chemical Society.

[10]  S. Schulman,et al.  Introduction to fluorescence spectroscopy , 1999 .

[11]  P. Bailey,et al.  Guanidines as neutral monodentate ligands; syntheses and crystal structures of [Co{PhN=C(NHPh)(2)}(2)Cl-2] and [Ag{PhN=C(NHPh)(2)}][SO3CF3] , 1997 .

[12]  K. Ghiggino,et al.  Synthesis, structural studies and photochemistry of cobalt(III) complexes of anthracenylcyclam macrocycles , 2003 .

[13]  L. Simándi Advances in catalytic activation of dioxygen by metal complexes , 2002 .

[14]  J. Lakowicz Principles of fluorescence spectroscopy , 1983 .

[15]  NO‐Erkennung durch einen Metallkomplex als Folge der selektiven Dissoziation eines Liganden , 2000 .

[16]  M. Licchelli,et al.  Redox Switching of Anthracene Fluorescence through the CuII/CuI Couple , 1995 .

[17]  V. Yam,et al.  Synthesis, photophysics, and electrochemistry of dinuclear cadmium(II) diimine complexes with bridging chalcogenolate ligands. X-Ray crystal structures of [(phen)2Cd(µ-SC6H4CH3-p)]2(PF6)2 and [(phen)2Cd(µ-SeC6H5)]2(PF6)2 , 1999 .

[18]  Sonja Herres-Pawlis,et al.  A Library of Peralkylated Bis‐guanidine Ligands for Use in Biomimetic Coordination Chemistry , 2005 .

[19]  Biao Wu,et al.  Synthesis, Characterization, and Ethylene Oligomerization and Polymerization of Ferrous and Cobaltous 2-(Ethylcarboxylato)-6-iminopyridyl Complexes , 2004 .

[20]  G. Bogdanović,et al.  Transition metal complexes with thiosemicarbazide-based ligands. Part L. Synthesis, physicochemical properties and crystal structures of Co(II) complexes with acetone S-methylisothiosemicarbazone , 2006 .

[21]  Suning Wang,et al.  Blue luminescent rigid molecular rods bearing N-7-azaindolyl and 2,2'-dipyridylamino and their Zn(II) and Ag(I) complexes. , 2003, Inorganic chemistry.