Molecular structures of Cu(II), Rh(III) complexes of 2-N substituted N-confused porphyrin inner C-oxide

Lin, Wen-Chain; Hsaio, De-Zhi; Chang, Wen-Pin; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

doi:10.1016/j.poly.2012.05.018

Cited by 10 publications

(13 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus,t he metal ion interacts with the C(21)À O(25) fragment in an h 2 fashion. The C(21)ÀO(25) distance of 1.343(6) i n3-Rh-CO resembles similard istances observed for Ni II ,F e II ,a nd Rh III complexes of 21-oxy N-confused porphyrins; [48][49][50] furthermore,t his distance is close to the CÀOb ond length of 1.336 (5) , which is typical of phenoxide ligands.…”

Section: Resultssupporting

confidence: 69%

See 1 more Smart Citation

From para‐Benziporphyrin to Rhodium(III) 21‐Carbaporphyrins: Imprinting Rh⋅⋅⋅η²‐CC, Rh⋅⋅⋅η²‐CO, and Rh⋅⋅⋅η²‐CH Coordination Motifs

Idec

Szterenberg

Latos‐Grażyński

2015

Chemistry A European J

View full text Add to dashboard Cite

Rhodium(III) para-benziporphyrin alters the fundamental reactivity of the built-in para-phenylene moiety. Due to additional macrocyclic stabilization, a sequence of intramolecular rearrangements are triggered to afford rhodium(III) 21-carbaporphyrin, which incorporates the rhodacyclopropane motif. The peculiar reversible transformations of the bridging methylene unit provide an example of selective and reversible aliphatic C-H bond elimination. Rhodium(III) 21-carbaporphyrin can be oxygenated to rhodium(III) 21-oxy-21-carbaporphyrin, whereas the metal ion interacts with the C(21)-O(25) fragment in an η(2) fashion. This species demonstrates a remarkable axial affinity toward alkenes.

show abstract

Section: Resultssupporting

confidence: 69%

“…The moleculars tructure of 3-Rh-CO ( Figure 4) resembles that of ar hodium(III)2 1-oxy N-confused porphyrin. [42,48] The RhÀ C (21) and RhÀO(25) distances are 2.099(2) and 2.035(2) , re-spectively,a nd are clearly within the limits of regularR h ÀCa nd RhÀOb onds. The environment of C(21) is only slightly tetrahedrally distorted.…”

Section: Resultsmentioning

confidence: 79%

From para‐Benziporphyrin to Rhodium(III) 21‐Carbaporphyrins: Imprinting Rh⋅⋅⋅η²‐CC, Rh⋅⋅⋅η²‐CO, and Rh⋅⋅⋅η²‐CH Coordination Motifs

Idec

Szterenberg

Latos‐Grażyński

2015

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…intensity): 835. A mixture of 2 (0.039 g, 0.04 mmol) and Ni(OAc) 2 (0.05 g, 0.20 mmol) were refluxed in CH 3 CN (10 ml) and CH 2 Cl 2 (10 ml) for 12 h. 3,4 After concentrating the reaction mixture, the residue was dissolved in 10 ml of CH 2 Cl 2 and filtered. The filtrate was concentrated and the residue was purified over a silica gel column (230-400 mesh, 50 g) using CH 2 Cl 2 as the eluent to yield a dark green solution of 7.…”

Section: Methodsmentioning

confidence: 99%

“…3 When the ethoxycarbonylmethyl group of 1 is modified to a bulky 3′-phenoxypropyl group, the free base 2-aza-(3′-phenoxypropyl)-5,10,15,20-tetraphenyl N-confused porphyrin, 2-NCH 2 CH 2 CH 2 OC 6 H 5 NCTPPH (2), is derived. 4 In this study, we focus on the alkyl group of 2-NCH 2 COOEtNCTPPH (1) and 2-NCH 2 CH 2 CH 2 OC 6 H 5 -NCTPPH (2). 4 Unlike the NH tautomerism that exists in NCTPPH 2 , the free base 1 (or 2) has only one stable form.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A 13C and 1H NMR spectroscopic investigation of the structure of the iminium ion with a dipolar form in metal complexes of 2-N-substituted N-confused porphyrins

et al. 2012

Self Cite

View full text Add to dashboard Cite

The crystal structures of chloro(2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) zinc(II) [Zn(2-NCH2COOC2H5NCTPP)Cl; 4], (2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) palladium(II) [Pd(2-NCH2COOC2H5NCTPP); 5], bromo(2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) manganese(III) [Mn(2-NCH2COOC2H5NCTPP)Br; 6], [2-aza-(3′-phenoxypropyl)-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′] nickel(II) [Ni(2-NCH2CH2CH2OC6H5NCTPP); 7] and chloro(2-aza-2-methoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) zinc(II) [Zn(2-NCH2COOCH3NCTPP)Cl; 8] have been established. The g value of 9.54, which was measured from the parallel polarization of the X-band EPR spectra in CHCl3 at 4 K, is consistent with the high spin mononuclear manganese(III) centre (S = 2) in 6. The magnitude of the axial (D) zero-field splitting (ZFS) for the mononuclear Mn(III) centre in 6 was determined approximately to be 1.63 cm(−1) by paramagnetic susceptibility measurements. The NMR spectroscopic investigation of the iminium ion with a dipolar canonical contribution to the metal complexes 5–7, Pd(2-NCH2C6H5NCTPP) (10) and Ni(2-NCH2C6H5NCTPP) (11) in CDCl3 is reported. A resonance between the dipolar canonical form II and covalent canonical form I exists for complexes 5–7, 10 and 11 in CDCl3. To develop the correlations between δ13C [C(3)], δ1H [H(3)] and the canonical form II in 5–7, 10 and 11, this work thoroughly examines the 13C and 1H NMR of N+=CH(Ar) fragment on seven metal complexes of 2-N substituted N-confused porphyrin. According to these results, the 13C [C(3)] and 1H [H(3)] chemical shifts of the N+=CH(Ar) fragment at 20 °C in CDCl3 are separately located at 152.6 ± 0.5 and 8.30 ± 0.15 ppm respectively for the iminium ion. This exists as a dipolar canonical form II for complexes 5–7, 10 and 11, and the N–CH(Ar) group appears at 121.1 ± 0.1 ppm and 6.35 ± 0.01 ppm, which is in a covalent canonical form I contribution to complexes 4 and 8. X-Ray diffraction data indicate that N(2)–C(3) = 1.315 ± 0.011 Å for the dipolar contribution of 5–7, 10–13, while N(2)–C(3) = 1.331 ± 0.008 Å for the covalent contribution of 4 and 8.

show abstract

2‐Aza‐21‐Carbaporphyrin in Construction of Chiral Supramolecular Assemblies

Koniarz¹,

Chmielewski²

2022

Chiral Building Blocks in Asymmetric Synthesis

View full text Add to dashboard Cite

Molecular structures of Cu(II), Rh(III) complexes of 2-N substituted N-confused porphyrin inner C-oxide

Cited by 10 publications

References 11 publications

From para‐Benziporphyrin to Rhodium(III) 21‐Carbaporphyrins: Imprinting Rh⋅⋅⋅η²‐CC, Rh⋅⋅⋅η²‐CO, and Rh⋅⋅⋅η²‐CH Coordination Motifs

From para‐Benziporphyrin to Rhodium(III) 21‐Carbaporphyrins: Imprinting Rh⋅⋅⋅η²‐CC, Rh⋅⋅⋅η²‐CO, and Rh⋅⋅⋅η²‐CH Coordination Motifs

A 13C and 1H NMR spectroscopic investigation of the structure of the iminium ion with a dipolar form in metal complexes of 2-N-substituted N-confused porphyrins

2‐Aza‐21‐Carbaporphyrin in Construction of Chiral Supramolecular Assemblies

Contact Info

Product

Resources

About

Molecular structures of Cu(II), Rh(III) complexes of 2-N substituted N-confused porphyrin inner C-oxide

Cited by 10 publications

References 11 publications

From para‐Benziporphyrin to Rhodium(III) 21‐Carbaporphyrins: Imprinting Rh⋅⋅⋅η2‐CC, Rh⋅⋅⋅η2‐CO, and Rh⋅⋅⋅η2‐CH Coordination Motifs

From para‐Benziporphyrin to Rhodium(III) 21‐Carbaporphyrins: Imprinting Rh⋅⋅⋅η2‐CC, Rh⋅⋅⋅η2‐CO, and Rh⋅⋅⋅η2‐CH Coordination Motifs

A 13C and 1H NMR spectroscopic investigation of the structure of the iminium ion with a dipolar form in metal complexes of 2-N-substituted N-confused porphyrins

2‐Aza‐21‐Carbaporphyrin in Construction of Chiral Supramolecular Assemblies

Contact Info

Product

Resources

About

From para‐Benziporphyrin to Rhodium(III) 21‐Carbaporphyrins: Imprinting Rh⋅⋅⋅η²‐CC, Rh⋅⋅⋅η²‐CO, and Rh⋅⋅⋅η²‐CH Coordination Motifs

From para‐Benziporphyrin to Rhodium(III) 21‐Carbaporphyrins: Imprinting Rh⋅⋅⋅η²‐CC, Rh⋅⋅⋅η²‐CO, and Rh⋅⋅⋅η²‐CH Coordination Motifs