Synthesis and Characterization of Some Copper(I) Phenanthroline Complexes

Pallenberg, Alexander J.; Koenig, Kristina S.; Barnhart, David M.

doi:10.1021/ic00115a009

Cited by 136 publications

(128 citation statements)

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“…Similar to these species, the cation in (Cu(ocp)2](BF4) is in a distorted tetrahe dral environment between two chelating heterocy cles with a dihedral angle of 88.9°. While the Cu-N bond distances are similar to those in 2,9-dialkyl derivatives [9,19], the bite angles N-Cu-N are a bit smaller (< 79°) than in these analogues (> 81°) [9,19,20]. The latter may reflect multiple close C l-C l contacts.…”

Section: Structure O F [ C U ( O C P ] ( Bf+ )*C H 2c Hmentioning

confidence: 89%

“…There are a number of structures available for substituted bis( 1,10-phenanthroline)copper(I) com plex cations [9,19,20]. Similar to these species, the cation in (Cu(ocp)2](BF4) is in a distorted tetrahe dral environment between two chelating heterocy cles with a dihedral angle of 88.9°.…”

Section: Structure O F [ C U ( O C P ] ( Bf+ )*C H 2c Hmentioning

confidence: 99%

“…The struc tures of such molecules are also of relevance for supramolecular chemistry, e.g. for the synthesis of catenates and knotted molecules [7], for the under standing of the coordination and functioning of cop per centers in proteins [8] and for potential medical applications [9], On the other hand, the interest in polychlorinated aromatics and their reactivity is prompted by at tempts to understand their behavior in the environ ment, i.e. their oxidative or hydrolytic degradation (or lack thereof) by enzymes such as cytochrome P-450 [10].…”

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confidence: 99%

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Polychlorinated Biaryl Heterocycles as Potential Ligands. Reactions between Octachloro-1,10-phenanthroline and -2,2′-bipyridine with Copper(I) and Other Metal Ions

Titze

Kaim

1996

Zeitschrift Für Naturforschung B

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C hlorinated A rom atics, C opper C om pounds, C rystal Structure, Electrochem istry, H eterocycles Perchlorinated derivatives o f the com m on a -d iim in e chelate ligands 2,2'-bipyridine and 1,10-phenanthroline w ere synthesized and tested fo r their coordination behavior tow ards metal ions. O ctachloro-l.lO -ph en an th ro lin e (ocp) was o b tained via chlorination with P C I5 under pressure (300°C, 18 h). It fails to form stable com plexes w ith e.g. Fe2+, M n2+, Ru2+, N i2+, Z n 2+ or Cd~+, but yields com plex cations [M (ocp)2]+ w ith M = Cu, Ag. The crystal structure an aly sis o f the red tetrafluoroborate o f the copper(I) com plex cation reveals a distorted tetrahedral coordination at the metal w ith a slight tendency tow ards the trigonal-pyram idal arrangem ent; two essentially planar ligands w ith sm all bite angles intersect at alm ost right angle. Relative to conventional bis( 1,10-phenanthroline)copper(I) com plexes with sim ilar structures, [C u(ocp)2]+ has oxidation and reduction potentials shifted positively by about 1 V which leaves the energy o f the m ain M LC T absorption features little changed. A ttem pts to synthesize R u C h (o c p )2 in D M F produced as substituted product a sym m etrical b is(dim ethylam ino)-hexachloro-l,10-phenanthroline w hich can be oxidized electrochem ically in tw o steps. In contrast to ocp, octachloro-2,2'-bipyridine (ocb) show ed no detectable com plexation with C u+ and a very neg ative reduction potential, most probably due to its inability to exhibit a low -energy coplanar conform ation.Transition metal complexes with perhalogenated ligands have been investigated as potential oxida tion catalysts [1], The reason is the lower activation of C-Hal vs. C-H bonds in highly oxidized interme diates towards dissociation, Hal+ ions being much poorer leaving groups than H+. Examples include especially macrocyclic ligands such as the por phyrins [1], Small perchlorinated aromatic ligands were also used to investigate unusual and normally very reactive oxidation states such as Pt(III) [2].Perhalogenated derivatives of the standard adiimine chelate ligands 2,2'-bipyridine (bpy) and 1, 10-phenanthroline (phen) have not yet been systematically studied although the parent com pounds and their organosubstituted derivatives were employed as ligands in arrangements for oxidation catalysis [3]. In particular, (1,10-phenanthroline)copper(I) complexes with their low-lying metal(d)-to-ligand(7r*) charge transfer * R eprint requests to Prof. Dr. W. Kaim.(MLCT) excited states have received wide attention because of their long-standing application in ana lytical chemistry [4] and their more recent uses as "chemical nucleases" in site-specific DNA cleavage [51 and as photoactivated catalysts [6]. The struc tures of such molecules are also of relevance for supramolecular chemistry, e.g. for the synthesis of catenates and knotted molecules [7], for the under standing of the coordination and functioning of cop per centers in proteins [8] and for potential medical applications [9],...

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Section: Structure O F [ C U ( O C P ] ( Bf+ )*C H 2c Hmentioning

confidence: 89%

Section: Structure O F [ C U ( O C P ] ( Bf+ )*C H 2c Hmentioning

confidence: 99%

mentioning

confidence: 99%

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Polychlorinated Biaryl Heterocycles as Potential Ligands. Reactions between Octachloro-1,10-phenanthroline and -2,2′-bipyridine with Copper(I) and Other Metal Ions

Titze

Kaim

1996

Zeitschrift Für Naturforschung B

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“…The average Cu-N distance in 3 (2.047(4) Å) is typical of Cu(I)-neocuproine type complexes. 37 However, the two Cu-S distances are quite different with Cu-S1: 2.2670 (16) …”

Section: (Et 4 N)[cu(neo)ni(nppeps)] (3)mentioning

confidence: 99%

Synthetic Analogues of the Active Site of the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase: Syntheses, Structures, and Reactions with CO

2006

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Two metallosynthons, namely (Et 4 N) 2 [Ni(NpPepS)] (1) and (Et 4 N) 2 [Ni(PhPepS)] (2) containing carboxamido-N and thiolato-S as donors have been used to model the bimetallic M p -Ni d subsite of the A-cluster of the enzyme ACS/CODH. A series of sulfurbridged Ni/Cu dinuclear and trinuclear complexes (3-10) have been synthesized to explore their redox properties and affinity of the metal centers toward CO. The structures of (Et 4 N) 2 (8), and [Ni(dppe)Ni(PhPepS)]•CH 2 Cl 2 (10•CH 2 Cl 2 ) have been determined by crystallography. The Ni d mimics 1 and 2 resist reduction and exhibit no affinity toward CO. In contrast, the sulfur-bridged Ni center (designated Ni C ) in the trinuclear models 5-8 are amenable to reduction and binds CO in the Ni(I) state. Also, the sulfurbridged Ni C center can be removed from the trimers (5-8) by treatment with 1,10-phenanthroline much like the "labile Ni" from the enzyme. The dinuclear Ni-Ni models 9 and 10 resemble the Ni p -Ni d subsite of the A-cluster more closely and only the modeled Ni p site of the dimers can be reduced. The Ni(I)-Ni(II) species display EPR spectra typical of a Ni(I) center in distorted trigonal bipyramidal and distorted tetrahedral geometries for 9 red and 10 red , respectively. Both species bind CO and the CO-adducts 9 red -CO and 10 red -CO display strong ν co at 2044 and 1997 cm -1 , respectively. The reduction of 10 is reversible. The CO-affinity of 10 in the reduced state and the ν co value of 10 red -CO closely resemble the CO-bound reduced A-cluster (ν co = 1996 cm -1 ).

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“…This increase in stretching frequency may be due to the conjugation caused by the ligand molecule. This has been confirmed by the absorption peaks present in the region of 1496-1442 and 1609-1518 cm -1 that may be assigned to ν(C C)/ν(C N) [36][37][38] ring vibrations of ligand moiety. Also, the peaks were comparatively broad which confirm the polymeric nature of these compounds.…”

Section: Resultsmentioning

confidence: 52%

Electrochemical Reactions of Aldehydes/Ketones at Sacrificial Nickel Anode: Synthesis and Characterization of Nickel(II) Glycolates and Their Coordination Complexes

Singh¹,

Kaur²

2018

Asian J. Chem.

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Synthesis and Characterization of Some Copper(I) Phenanthroline Complexes

Cited by 136 publications

References 0 publications

Polychlorinated Biaryl Heterocycles as Potential Ligands. Reactions between Octachloro-1,10-phenanthroline and -2,2′-bipyridine with Copper(I) and Other Metal Ions

Polychlorinated Biaryl Heterocycles as Potential Ligands. Reactions between Octachloro-1,10-phenanthroline and -2,2′-bipyridine with Copper(I) and Other Metal Ions

Synthetic Analogues of the Active Site of the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase: Syntheses, Structures, and Reactions with CO

Electrochemical Reactions of Aldehydes/Ketones at Sacrificial Nickel Anode: Synthesis and Characterization of Nickel(II) Glycolates and Their Coordination Complexes

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