Metalloprophyrins containing .sigma.-bonded nitrogen axial ligands. 2. Synthesis and characterization of iron(III) tetrazolato and triazolato porphyrin complexes. Molecular structure of (5-methyltetrazolato)(2,3,7,8,12,13,17,18-octaethylporphinato)iron(III)

Guilard, Roger; Perrot, I.; Tabard, Alain; Richard, Philippe; Lecomte, Claude; Liu, Y. H.; Kadish, Karl M.

doi:10.1021/ic00001a007

Cited by 44 publications

(16 citation statements)

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“…4 In a previous study, 5 we have studied mononuclear and dinuclear iridium(III) 5-methyltetrazolate (MeCN 4 − ) complexes, bearing 2,2′-bipyridine (bpy), N,N-dimethyldithiocarbamate (Me 2 dtc − ) or 2-pyridylthiolate ( pyS − ) as an ancillary ligand, because MeCN 4 − is a versatile multidentate ligand to give a variety of linkage and bridging isomers (Scheme 1). [6][7][8][9][10][11][12][13][14] In mononuclear complexes, MeCN 4 − was bound to the Ir III centre through the N 1 atom (-κN 1 ) in the Me 2 dtc complex, [Cp*Ir(Me 2 dtc)(MeCN 4 )], while it coordinated via the N 2 atom (-κN 2 ) in the bpy complex, [Cp*Ir(bpy)(MeCN 4 )]PF 6 (1). The crystal structures of the dinuclear complexes of [{Cp*Ir-(bpy)} 2 (μ-MeCN 4 )](PF 6 ) 3 (5), [{Cp*Ir(Me 2 dtc)} 2 (μ-MeCN 4 )]PF 6 and [(Cp*Ir) 2 (μ-pyS) 2 (μ-MeCN 4 )]PF 6 revealed that MeCN 4 − took μ-κN 1 :κN 3 , μ-κN 1 :κN 4 and μ-κN 2 :κN 3 bridging modes, respectively, in these complexes.…”

Section: Introductionmentioning

confidence: 99%

Comparison of ancillary ligand effects between 2,2′-bipyridine and 2-(2′-pyridyl)phenyl in the linkage and bridging isomerism of 5-methyltetrazolato iridium(iii) and/or rhodium(iii) complexes

et al. 2013

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Several new iridium(III) and rhodium(III) complexes bearing 5-methyltetrazolate (MeCN4(-)) have been prepared, and their structures in the crystals and in solution have been determined by X-ray analysis and by NMR spectroscopy, respectively. In the crystals of the mononuclear complexes, κN(2)-coordination of MeCN4(-) was observed when the ancillary ligand was 2,2'-bipyridine (bpy): [Cp*M(bpy)(MeCN4-κN(2))]PF6 (Cp* = η(5)-C5Me5; M = Ir: 1 and Rh: 2), while the corresponding complexes with 2-(2'-pyridyl)phenyl (ppy(-)) were confirmed to have the κN(1)-coordination of MeCN4(-): [Cp*M(ppy)(MeCN4-κN(1))] (M = Ir: 3 and Rh: 4). In solution, the Ir(III) complexes (1 and 3) were robust enough to maintain their molecular structures, but the Rh(III) complexes (2 and 4) existed as an equilibrium mixture of the κN(1)- and κN(2)-isomers. In addition to the Ir(III)-Ir(III) and Rh(III)-Rh(III) homodinuclear complexes bridged by MeCN4(-) (5-8), the corresponding heterodinuclear Ir(III)-Rh(III) complexes (9-12) were prepared using the mononuclear Ir(III) complexes (1 and 3) as precursors. The molecular structures of these dinuclear complexes were also characterised. Interestingly, both of the heterodinuclear complexes comprised of Cp*M(bpy)(2+) and Cp*M'(ppy)(+) fragments, [Cp*M(bpy)(μ-MeCN4)M'(ppy)Cp*](PF6)2 (M = Ir, M' = Rh: 10 and M = Rh, M' = Ir: 11), exhibited selective crystallisation of a specific μ-κN(1)(M'-ppy):κN(3)(M-bpy) isomer. In solution, the dinuclear complexes with a Rh-N(MeCN4) bond and more than one positive charge (6 and 9-11) showed a dissociation equilibrium, while monocationic MeCN4-bridged complexes (7, 8 and 12) were inactive for dissociation. Furthermore, the heterodinuclear complexes of 9-12, as well as the Rh(III)-Rh(III) complex of 8, exhibited a bridging isomerisation, which would proceed via a η(2):η(2)-intermediate without dissociation of Cp*M(bpy or ppy) fragments.

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Section: Introductionmentioning

confidence: 99%

Comparison of ancillary ligand effects between 2,2′-bipyridine and 2-(2′-pyridyl)phenyl in the linkage and bridging isomerism of 5-methyltetrazolato iridium(iii) and/or rhodium(iii) complexes

et al. 2013

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“…It is characterized by factors g z % 2.9, g y % 2.3 and g x % 1.57. The second set indicates a high-spin component, which is typical for high-spin (S = 5/2) iron ions in complexes with axial symmetry (g c % 6 and g k % 2) [22,[24][25][26]31].…”

Section: Discussionmentioning

confidence: 99%

Solution Coordination Chemistry of Protohaemin IX Peptide Derivatives

Rozhkova

Evstigneeva

Nemykin³

1999

J. Porphyrins Phthalocyanines

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As part of an investigation aimed at developing artificial models for mimicking haemoprotein activity, four C-aminoacyl protohaemin IX derivatives with one or two -L-Leu-L- HisOMe (complexes 3 and 1) or -β-Ala-L- HisOMe (complexes 4 and 2) peptide fragments have been studied by means of electronic and ESR spectroscopy. The bis-His complexes 1 and 2 are predominantly low-spin ( S = 1/2) species, while the mono-His complexes 3 and 4 are predominantly high-spin ( S = 5/2) species. Products of the treatment of starting complexes 1–4 with trichloroacetic acid, acetic acid, methylimidazole, sodium cyanide and sodium hydroxide have been analysed by electronic spectroscopy. Weak-field ligands lead to predominantly high-spin hexacoordinated complexes, while strong-field ligands result in predominantly low-spin ones.

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“… 3 Metal azido complexes have a rich cycloaddition chemistry. 4 – 6 A range of d-block azido complexes, including those of Mn( i ), 7 , 8 Fe( iii ), 9 Pd( ii ), 10 Pt( ii ), 10 – 15 Rh( iii ) 16 and Au( i ), 17 have been reported to undergo copper-free 1,3-dipolar cycloaddition or “click” reactions with carbon–carbon and carbon-heteroatom functional groups such as alkynes, isocyanides, isonitriles, nitriles, carbon disulphides and isothiocyanates. Electron-deficient alkynes such as dimethyl acetylenedicarboxylate (DMAD) and diethyl acetylenedicarboxylate (DEACD) are relatively reactive: Mo( ii ), 16 , 18 Co( iii ), 19 Fe( iii ) 19 , 20 Ru( ii ), 20 – 25 Pd( ii ) 26 – 28 and Ta 29 azido complexes all react with DMAD.…”

Section: Introductionmentioning

confidence: 99%