Synthesis and the Structure of a Thiolato Amine Nickel Complex. (N,N′-Ethylenebis(o-mercaptobenzylaminato))nickel(II)

Yamamura, Takeshi; Tadokoro, Makoto; Hamaguchi, Miho; Kuroda, Reiko

doi:10.1246/cl.1989.1481

Cited by 7 publications

(7 citation statements)

References 20 publications

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“…[112,125] Thus, the slightly shorter CÀS and NiÀS distances are consistent in the series of complexes of thiosalan, thiosalen, and thiotriplesalen. [112,125] Thus, the slightly shorter CÀS and NiÀS distances are consistent in the series of complexes of thiosalan, thiosalen, and thiotriplesalen.…”

Section: Heteroradialene Character In Extended Thiophloroglucinol Ligsupporting

confidence: 60%

“…For comparison of the Ni À S distances, the values of saturated Ni II thiosalan complexes are of interest: dA C H T U N G T R E N N U N G (Ni À S) = 2.17 , dA C H T U N G T R E N N U N G (Ni À N) = 1.95 , dA C H T U N G T R E N N U N G (C À S) = 1.76 . [112,125] Thus, the slightly shorter CÀS and NiÀS distances are consistent in the series of complexes of thiosalan, thiosalen, and thiotriplesalen. Interestingly, they fall also in the range of NiÀS and SÀ C distances of Ni II complexes with noninnocent o-iminothionebenzosemiquinonate [126] and o-dithiobenzosemiquinonate radical [127] ligands.…”

Section: Heteroradialene Character In Extended Thiophloroglucinol Ligmentioning

confidence: 63%

“…For comparison of the NiS distances, the values of saturated Ni II thiosalan complexes are of interest: d (NiS)=2.17 Å, d (NiN)=1.95 Å, d (CS)=1.76 Å 112. 125 Thus, the slightly shorter CS and NiS distances are consistent in the series of complexes of thiosalan, thiosalen, and thiotriplesalen.…”

Section: Analysis and Discussionmentioning

confidence: 99%

“…[108][109][110][111][112][113] The CS resonances in the thiophloroglucinol systems shift from about 189 to about 155 ppm on complexation, whereas the CO resonances in the phloroglucinol systems shift from about 185 to about 170 ppm. [108][109][110][111][112][113] The CS resonances in the thiophloroglucinol systems shift from about 189 to about 155 ppm on complexation, whereas the CO resonances in the phloroglucinol systems shift from about 185 to about 170 ppm.…”

Section: Heteroradialene Character In Extended Thiophloroglucinolmentioning

confidence: 99%

“…Comparisons for the evaluation of the change in the heteroradialene character in the thiophloroglucinol ligands on complexation are limited, as the chemical shifts for the mononuclear Ni II thiosalen complexes are not assigned if provided at all. [108][109][110][111][112][113] The CS resonances in the thiophloroglucinol systems shift from about 189 to about 155 ppm on complexation, whereas the CO resonances in the phloroglucinol systems shift from about 185 to about 170 ppm. This much Scheme 3.…”

Section: Heteroradialene Character In Extended Thiophloroglucinol Commentioning

confidence: 99%

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Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes

Feldscher¹,

Stammler²,

Bögge³

et al. 2014

Chemistry An Asian Journal

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Extended phloroglucinol ligands and complexes are best described as nonaromatic heteroradialenes. Herein, the electronic structures of extended thiophloroglucinol ligands and their Ni(II) 3 complexes are evaluated by comparison to their phloroglucinol analogs by means of NMR, FTIR, UV/Vis, and structural parameters. To provide a full set of compounds for this comparison of S versus O substitution, a new triplesalen ligand, its Ni(II) 3 complex, and a new thiophloroglucinol were synthesized. (1) H and (15) N NMR chemical shifts and coupling constants prove that the thiophloroglucinol ligands exist as the N-protonated and not the O-protonated tautomer. (13) C and (15) N NMR chemical shifts and structural parameters further demonstrated that the extended thiophloroglucinol ligands must be described with a predominant thione-enamine (heteroradialene) character despite the participation of a CS double bond. In the Ni(II) 3 complexes, this heteroradialene character is reduced but still predominant.

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Section: Heteroradialene Character In Extended Thiophloroglucinol Ligsupporting

confidence: 60%

Section: Heteroradialene Character In Extended Thiophloroglucinol Ligmentioning

confidence: 63%

Section: Analysis and Discussionmentioning

confidence: 99%

Section: Heteroradialene Character In Extended Thiophloroglucinolmentioning

confidence: 99%

Section: Heteroradialene Character In Extended Thiophloroglucinol Commentioning

confidence: 99%

See 3 more Smart Citations

Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes

Feldscher¹,

Stammler²,

Bögge³

et al. 2014

Chemistry An Asian Journal

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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 Coordination Chemistry with Oxothiolate Ligands and Its Relevance to Hydrogenase Enzymes

Chou

Varotsis

Kanatzidis

1995

Bioinorganic Chemistry

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Synthesis and the Structure of a Thiolato Amine Nickel Complex. (N,N′-Ethylenebis(o-mercaptobenzylaminato))nickel(II)

Cited by 7 publications

References 20 publications

Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes

Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes

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

Nickel Coordination Chemistry with Oxothiolate Ligands and Its Relevance to Hydrogenase Enzymes

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