Inner C-arylation of a doubly N-confused porphyrin–Pd complex in toluene—the possibility of a Pd3+ intermediate

Furuta, Hiroyuki; Maeda, Hiromitsu; Osuka, Atsuhiro; Yasutake, Mikio; Shinmyozu, Teruo; Ishikawa, Yuichi

doi:10.1039/b003022h

Cited by 64 publications

(51 citation statements)

References 13 publications

(11 reference statements)

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“…While only a preliminary crystal structure was obtained for 12 (Supporting Information), the structure of 13 has been determined by using X-ray diffraction analysis ( Figure 6). In the latter, the Cu ion resides in the familiar porphyrin-like core consisting of pyrroles A, B, H, and I, the Pd1 ion is bound by C23, N6, N7, and C37 in an NNCC fashion analogous to doubly N-confused porphyrin-like coordination, [15] and the Pd2 ion is bound by N3, N4, and C22. Interestingly, the distance between Pd2 and C38 is 2.23 , which is distinctly longer than a normal C À Pd bond length, but is exactly what one would expect for an agostic interaction, thus suggesting an agostic interaction between Pd2 and the CÀH bond of pyrrole H. [16] As a consequence of the coordination of the two palladium ions, the tetrapyrrolic segment consisting of pyrroles D, E, F, and G becomes more coplanar in 13, with a mean plane deviation of 0.12 , while pyrrole H is tilted at a dihedral angle of 33.68.…”

Section: ([Màh]mentioning

confidence: 99%

[40]Nonaphyrin(1.1.1.1.1.1.1.1.1) and Its Heterometallic Complexes with Palladium–Carbon Bonds

Kamimura

Shimizu

Osuka

2007

Chemistry A European J

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meso-Pentafluorophenyl- substituted [40]nonaphyrin(1.1.1.1.1.1.1.1.1) 3 has been prepared by using a stepwise ring-size-selective synthesis, and has been reduced with NaBH(4) to [42]nonaphyrin(1.1.1.1.1.1.1.1.1) 5. Structurally, 3 is characterized by a figure-of-eight shape, consisting of a porphyrin-like tetrapyrrolic segment and a hexaphyrin-like hexapyrrolic segment, whereas 5 has been found to adopt a distorted nonplanar butterfly-like shape. In the mono-metal complexes 6 and 7, a Zn(II) or Cu(II) ion is bound by the porphyrin-like tetrapyrrolic segment, maintaining the overall structure of 3. Similarly to 3, complexes 6 and 7 are interconvertible with the corresponding complexes 9 and 10 through two-electron reduction with NaBH(4) and oxidation with DDQ. The metal-free hexaphyrin-like segments of 6 and 7 have been shown to serve as a suitable platform for the complexation of two palladium ions, providing hetero-trinuclear metal complexes 11 (Zn(II)-Pd(II)-Pd(II)) and 13 (Cu(II)-Pd(II)-Pd(II)) in high yields, in which the Zn or Cu ion resides at the same porphyrin-like segment, and one Pd ion is bound in an NNCC fashion through double C--H bond activation while the other is bound in an NNC fashion with single C--H bond activation. Multi-metal complexes 11, 12, and 13 exhibit small electrochemical HOMO-LUMO gaps (<0.6 eV), despite their nonplanar conformations.

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Section: ([Màh]mentioning

confidence: 99%

[40]Nonaphyrin(1.1.1.1.1.1.1.1.1) and Its Heterometallic Complexes with Palladium–Carbon Bonds

Kamimura

Shimizu

Osuka

2007

Chemistry A European J

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“…Thus, the aromaticity observed for 8 does not result from the energetic preferences of the ligand facilitating hypothetically (trigonal to tetrahedral prearrangement step in coordination) but rather from the strong coordination of the gold(III) ion as documented by the remarkable relocation of C(22) resonance ( δ 22 =51.8 ppm) once compared to its position C(22)‐Me ( δ 22 =109.6 ppm) of 7 , respectively, which is quite typical for substituted carbon donors in carbaporphyrinoid complexes . The coordination motif of 8 resembles the side‐on coordination modes reported for N ‐alkyl porphyrins and C(21)‐methylated N‐confused porphyrins . Originally, Van Koten and co‐workers provided an important precedent for this type of coordination .…”

Section: Resultsmentioning

confidence: 87%

Gold(III) Triggered Transformations of 22‐Methyl‐m‐benziporphyrin Involving an Effective Contraction of Benzene to Cyclopentadiene

Hurej

Pawlicki

Latos‐Grażyński

2016

Chemistry A European J

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“…For the dimerization of Fe II complex eration [43]. With Pd II salts, cis-N 2 CP 8 forms a distorted square-planar Pd II complex (8-Pd II ), where the toluene is connected at one of the inner carbons [44]. In the case of Rh salts, 8 forms Rh I complex using two inner N and CO, not inner carbons [45], as seen in the Rh I coordination of NCP [35].…”

Section: Metal-coordinated Dimers Of N-confused Porphyrinmentioning

confidence: 99%

A dozen years of N-confusion: From synthesis to supramolecular chemistry

Maeda

Furuta

2006

Pure and Applied Chemistry

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The chemistry of N-confused porphyrin (NCP) and its analogs started in 1994. Since then, considerable progress has been made in understanding the unique properties of NCP and its analogs, which confer characteristic reactivity and metal complex formation. The evolved isomers, multiply NCPs, and expanded N-confused derivatives, have opened up new realms of NCP chemistry. Cis-and trans-doubly N-confused porphyrin (N 2 CP) stabilizes higher oxidation states such as Cu III in square-planar fashion in the core. Confused isomers with five or more pyrrole rings can coordinate several cations owing to their larger cavities compared to tetrapyrrolic system. The peripheral nitrogen(s) of NCP and its analogs can serve as hydrogen-bonding donor and acceptor, and metal coordination site as well. For example, NCP forms versatile dimers with the assistance of metal ions. The square-planar divalent metal complexes of C 6 F 5 -substituted NCP act as efficient anion-binding receptors. Furthermore, Cu III complexes of N 2 CP, possessing both N and NH at the periphery, form self-assembled one-dimensional (1D) hydrogen-bonding networks, whose orientations differ in cis (zigzag) and trans (straight) isomers.

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Inner C-arylation of a doubly N-confused porphyrin–Pd complex in toluene—the possibility of a Pd3+ intermediate

Cited by 64 publications

References 13 publications

[40]Nonaphyrin(1.1.1.1.1.1.1.1.1) and Its Heterometallic Complexes with Palladium–Carbon Bonds

[40]Nonaphyrin(1.1.1.1.1.1.1.1.1) and Its Heterometallic Complexes with Palladium–Carbon Bonds

Gold(III) Triggered Transformations of 22‐Methyl‐m‐benziporphyrin Involving an Effective Contraction of Benzene to Cyclopentadiene

A dozen years of N-confusion: From synthesis to supramolecular chemistry

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