Nickel‐, Palladium‐ und Platinkomplexe funktionalisierter Makrocyclen. Die Kristallstrukturen von [Ni(py2‐tasn)(H2O)](ClO4)2, [Pd(py2‐tasn)](PF6)2 und [Pt(py2‐tasn)](PF6)2. (py2‐tasn=4,7‐Bis(2‐methylpyridyl)‐1‐thia‐4,7‐diazacyclononan

Wasielewski, Klaus; Mattes, R.

doi:10.1002/zaac.19936190126

Cited by 17 publications

(1 citation statement)

References 7 publications

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“…In case of the L N2S complexes we were not able to obtain crystals so far. Nonetheless, crystal structures have been reported for similar Fe II and Ni II complexes (Wasielewski and Mattes, 1993;Zhang et al, 1998).…”

Section: Crystallographymentioning

confidence: 99%

Sensitized Photocatalytic CO2 Reduction With Earth Abundant 3d Metal Complexes Possessing Dipicolyl-Triazacyclononane Derivatives

et al. 2021

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Complexes based on nitrogen and sulfur containing ligands involving 3d metal centers are known for the electrocatalytic reduction of CO2. However, photocatalytical activation has rarely been investigated. We herein present results on the light-driven CO2 reduction using either Ir(dFppy)3 [Ir, dFppy = 2-(4,6-difluorophenyl)pyridine] or [Cu(xant)(bcp)]+, (Cu, xant = xantphos, bcp = bathocuproine) as photosensitizer in combination with TEA (triethylamine) as sacrificial electron donor. The 3d metal catalysts have either dptacn (dipicolyl-triazacyclononane, LN3) or dpdatcn (dipicolyl-diazathiocyclononane, LN2S) as ligand framework and Fe3+, Co3+ or Ni2+ as central metal ion. It turned out that the choice of ligand, metal center and solvent composition influences the selectivity for product formation, which means that the gaseous reduction products can be solely CO or H2 or a mixture of both. The ratio between these two products can be controlled by the right choice of reaction conditions. With using Cu as photosensitizer, we could introduce an intermolecular system that is based solely on 3d metal compounds being able to reduce CO2.

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Section: Crystallographymentioning

confidence: 99%

Sensitized Photocatalytic CO2 Reduction With Earth Abundant 3d Metal Complexes Possessing Dipicolyl-Triazacyclononane Derivatives

et al. 2021

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Synthese und Struktur der Cobalt(III)‐Komplexe 14gliedriger cis‐ und trans‐N₂S₂‐Dibenzomakrocyclen mit zwei koordinierenden Acetatogruppen

Ehlers

Funkemeier

Mattes

1994

Zeitschrift anorg allge chemie

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Die beiden isomeren Liganden 6,7,9,15,16,18‐Hexahydrodibenzo[f,m][1,8]dithia[4,11]diazacyclotetradecin‐8,17‐diessigsäure‐0,5‐hydrat (H2L3), C22H26N2O4S2 · 0,5 H2O bzw. 6,7,13,15,16,18‐Hexahydrodibenzo[e,m][1,4]dithia‐[8,11]diazacyclotetradecin‐14,17‐diessigsäure‐1,5‐hydrat (H2L6), C22H26N2O4S2 · 1,5 H2O mit cis‐ bzw. trans‐N2S2‐Donorzentren im vierzehngliedrigen makrocyclischen Ring und zwei Acetat‐Seitenketten bilden die stabilen Komplexe [Co(L3)]ClO4 · 2H2O (1) und [Co(L6)]ClO4 · H2O (2). CoIII ist jeweils von allen 6 Donorzentren der Liganden oktaedrisch umgeben. Die Liganden sind gefaltet. Die Metallatome liegen außerhalb der makrocyclischen Kavität. Kristalldaten: 1, monoklin, Raumgruppe C2/c, a = 3 797,7(9), b = 763,8(3), c = 2 207,0(7) pm, β = 123,17(2)°, Z = 8, 3 445 Reflexe, R(Rw) = 0,072(0,070); 2, monoklin, Raumgruppe C2/c, a = 3 197,1(6), b = 880,4(2), c = 1 890,6(4) pm, β = 112,19(3)°, Z = 8, 4415 Reflexe, R(Rw) = 0,062(0,064).

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Synthesis and Crystal Structures of Palladium(II) Complexes of Macrobicyclic Azathiaether Ligands

Siedle

Kersting

2003

Zeitschrift anorg allge chemie

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The macrobicyclic azathioether ligands L1 and L2 were investigated regarding their capability to form complexes with divalent palladium. L1 represents a cyclophane‐like ligand system comprising two 4‐tert‐butyl‐2, 6‐bis(aminomethyl)thiophenolate units, which are linked by an ethylene and two 3‐aza‐1, 5‐pentylene units to give two seventeen‐membered dithia‐triaza crowns fused at the common ArSCH2CH2SAr fragment. L2 is the hexa‐N‐methylated derivative of L1. Treatment of L1 and L2 with two equivalents of [PdCl2(CH3CN)2] gave the new complexes [(L1)Pd2Cl]+ (1) and [(L2)Pd2Cl2]2+ (2), respectively, which were isolated as perchlorate salts and characterized by elemental analysis, IR and NMR spectroscopy and by X‐ray crystallography. In 1, L1 acts as a septadentate ligand to give two distorted square‐planar PdN3S and PdN3Cl units, respectively. The structure of 2 shows L2 to be hexacoordinate, yielding two distorted square‐planar PdN2SCl units leaving two NMe groups dangling. NMR spectroscopic studies reveal that both complexes retain their solid‐state structures in solution. The reaction of L2 with one equivalent of [PdCl2(CH3CN)2] is accompanied by a bond cleavage reaction of one of the two aliphatic thioether bonds to afford the dinuclear complex [(L3)Pd2Cl2]Cl (3·Cl) of the ring‐opened 24‐membered hexaaza‐vinylthioether/thiophenolate derivative (L3)‐. The crystal structure determination of 3·Cl reveals two distorted‐square planar PdN2ClS units which are bridged by the thiophenolate sulfur atom of (L3)‐. The vinyl‐thioether moiety and the two remaining amine donors of (L3)‐ do not interact with the two palladium ions. The X‐ray structure analysis of the free macrocycle L2 demonstrates that the C‐S bond lengths become elongated upon coordination to the palladium(II) ions.

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Nickel‐, Palladium‐ und Platinkomplexe funktionalisierter Makrocyclen. Die Kristallstrukturen von [Ni(py₂‐tasn)(H₂O)](ClO₄)₂, [Pd(py₂‐tasn)](PF₆)₂ und [Pt(py₂‐tasn)](PF₆)₂. (py₂‐tasn=4,7‐Bis(2‐methylpyridyl)‐1‐thia‐4,7‐diazacyclononan

Cited by 17 publications

References 7 publications

Sensitized Photocatalytic CO2 Reduction With Earth Abundant 3d Metal Complexes Possessing Dipicolyl-Triazacyclononane Derivatives

Sensitized Photocatalytic CO2 Reduction With Earth Abundant 3d Metal Complexes Possessing Dipicolyl-Triazacyclononane Derivatives

Synthese und Struktur der Cobalt(III)‐Komplexe 14gliedriger cis‐ und trans‐N₂S₂‐Dibenzomakrocyclen mit zwei koordinierenden Acetatogruppen

Synthesis and Crystal Structures of Palladium(II) Complexes of Macrobicyclic Azathiaether Ligands

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Nickel‐, Palladium‐ und Platinkomplexe funktionalisierter Makrocyclen. Die Kristallstrukturen von [Ni(py2‐tasn)(H2O)](ClO4)2, [Pd(py2‐tasn)](PF6)2 und [Pt(py2‐tasn)](PF6)2. (py2‐tasn=4,7‐Bis(2‐methylpyridyl)‐1‐thia‐4,7‐diazacyclononan

Cited by 17 publications

References 7 publications

Sensitized Photocatalytic CO2 Reduction With Earth Abundant 3d Metal Complexes Possessing Dipicolyl-Triazacyclononane Derivatives

Sensitized Photocatalytic CO2 Reduction With Earth Abundant 3d Metal Complexes Possessing Dipicolyl-Triazacyclononane Derivatives

Synthese und Struktur der Cobalt(III)‐Komplexe 14gliedriger cis‐ und trans‐N2S2‐Dibenzomakrocyclen mit zwei koordinierenden Acetatogruppen

Synthesis and Crystal Structures of Palladium(II) Complexes of Macrobicyclic Azathiaether Ligands

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Nickel‐, Palladium‐ und Platinkomplexe funktionalisierter Makrocyclen. Die Kristallstrukturen von [Ni(py₂‐tasn)(H₂O)](ClO₄)₂, [Pd(py₂‐tasn)](PF₆)₂ und [Pt(py₂‐tasn)](PF₆)₂. (py₂‐tasn=4,7‐Bis(2‐methylpyridyl)‐1‐thia‐4,7‐diazacyclononan

Synthese und Struktur der Cobalt(III)‐Komplexe 14gliedriger cis‐ und trans‐N₂S₂‐Dibenzomakrocyclen mit zwei koordinierenden Acetatogruppen