[5,15-Bis(2-methylpropyl)porphyrinato]nickel(II)

Senge, Ma­thias O.

doi:10.1107/s1600536812035726

Cited by 3 publications

(6 citation statements)

References 11 publications

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“…Thus, the predicted mixture of ruf and dom distortions for NiD(alkyl)P might originate from a shortcoming of MM calculations. For the series of NiD(alkyl)P porphyrins investigated only the crystal structure of NiD(2-Me-Pr)P has been reported [89]. However, this compound forms π-π-dimers, which leads to an almost planar macrocycle.…”

Section: Nid(alkyl)p and Nit(alkyl)p Porphyrinsmentioning

confidence: 99%

“…The structures of the nickel porphyrins investigated -derived from our DFT calculations -are compared to reported crystal structures which are taken from the Cambridge Structural Database (respective CSD entry given in parenthesis) [108] and analyzed by NSD: NiD(2-Me-Pr)P (QEBXUS) [89], NiTPP (ZZZUUC01) [93], NiT(4-MeOPh)P (OROJUB) [94], NiT(2-Me-Pr)P (DOWCAT) [91],…”

Section: X-ray Crystallographic Datamentioning

confidence: 99%

“…Displacements along the lowest-frequency oop normal coordinates for NiD(alkyl)P porphyrins: sad (black), ruf (red), dom (blue), wav(x) (magenta), wav(y) (olive) and pro (navy). Structures are calculated with DFT (this study) and compared to reported MM calculations (values taken from literature)[67] and to crystal structures (X-ray): NiD(2-Me-Pr)P (two conformers in unit cell)[89], NiD(iPr)P[65], NiD(tBu)P[67].…”

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confidence: 99%

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Sterically induced distortions of nickel(II) porphyrins – Comprehensive investigation by DFT calculations and resonance Raman spectroscopy

Schindler

Kupfer

Ryan

et al. 2018

Coordination Chemistry Reviews

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nickel(II) porphyrins in dichloromethane is reported to comprehensively access their sterically induced distortions from planarity. Thus, the tutorial review focuses on both resonance Raman spectroscopic investigations and structural investigations based on DFT. We relate different theoretical and experimental methodologies to predict out-of-plane distortions of the porphyrin macrocycles which are quantified by normal-coordinate structural decomposition. This comprehensive compilation reveals shortcomings in the molecular mechanic calculations and illustrates the impact of crystal packing forces on crystal structures. Non-planar distortions shift the experimentally observed resonance Raman marker bands v 2 , v 3 and v 4 to lower frequency. A revised correlation between this shift and the calculated structural parameter (ruffling angle) is presented and reveals deviations from reported correlations based on molecular mechanics.

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Section: Nid(alkyl)p and Nit(alkyl)p Porphyrinsmentioning

confidence: 99%

Section: X-ray Crystallographic Datamentioning

confidence: 99%

mentioning

confidence: 99%

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Sterically induced distortions of nickel(II) porphyrins – Comprehensive investigation by DFT calculations and resonance Raman spectroscopy

Schindler

Kupfer

Ryan

et al. 2018

Coordination Chemistry Reviews

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“…Note, that compound (I), i.e. the meso disubstituted precursor compound, exhibits a planar macrocycle (Senge, 2012).…”

Section: Methodsmentioning

confidence: 99%

“…For the handling of crystals, see: Hope (1994). For related structures, see: Senge et al (1999); Senge (2012).…”

Section: Related Literaturementioning

confidence: 99%

(5-n-Butyl-10,20-diisobutylporphyrinato)nickel(II)

Senge¹,

Dahms²

2014

Acta Cryst E

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The asymmetric unit of the title compound, [Ni(C32H36N4)], contains two independent molecules exhibiting an overall ruffled conformation of the porphyrin macrocycle and differing mainly in the positions of the methyl groups. The average Ni—N bond lengths are 1.912 (2) and 1.910 (2) Å in the two molecules. The molecules form a closely spaced lattice structure in which neighbouring porphyrins are oriented in a nearly perpendicular fashion to each other. The compound was prepared via nucleophilic substitution of (5,15-diisobutylporphyrinato)nickel(II) with n-butyllithium.

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Conformational control of cofactors in nature – the influence of protein-induced macrocycle distortion on the biological function of tetrapyrroles

2015

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Tetrapyrrole-containing proteins are one of the most fundamental classes of enzymes in nature and it remains an open question to give a chemical rationale for the multitude of biological reactions that can be catalyzed by these pigmentprotein complexes. There are many fundamental processes where the same (i.e., chemically identical) porphyrin cofactor is involved in chemically quite distinct reactions. For example, heme is the active cofactor for oxygen transport and storage (hemoglobin, myoglobin) and for the incorporation of molecular oxygen in organic substrates (cytochrome P 450 ). It is involved in the terminal oxidation (cytochrome c oxidase) and the metabolism of H 2 O 2 (catalases and peroxidases) and catalyzes various electron transfer reactions in cytochromes. Likewise, in photosynthesis the same chlorophyll cofactor may function as a reaction center pigment (charge separation) or as an accessory pigment (exciton transfer) in light harvesting complexes (e.g., chlorophyll a). Whilst differences in the apoprotein sequences alone cannot explain the often drastic differences in physicochemical properties encountered for the same cofactor in diverse protein complexes, a critical factor for all biological functions must be the close structural interplay between bound cofactors and the respective apoprotein in addition to factors such as hydrogen bonding or electronic effects. Here, we explore how nature can use the same chemical molecule as a cofactor for chemically distinct reactions using the concept of conformational flexibility of tetrapyrroles. The multifaceted roles of tetrapyrroles are discussed in the context of the current knowledge on distorted porphyrins. Contemporary analytical methods now allow a more quantitative look at cofactors in protein complexes and the development of the field is illustrated by case studies on hemeproteins and photosynthetic complexes. Specific tetrapyrrole conformations are now used to prepare bioengineered designer proteins with specific catalytic or photochemical properties.

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[5,15-Bis(2-methylpropyl)porphyrinato]nickel(II)

Cited by 3 publications

References 11 publications

Sterically induced distortions of nickel(II) porphyrins – Comprehensive investigation by DFT calculations and resonance Raman spectroscopy

Sterically induced distortions of nickel(II) porphyrins – Comprehensive investigation by DFT calculations and resonance Raman spectroscopy

(5-n-Butyl-10,20-diisobutylporphyrinato)nickel(II)

Conformational control of cofactors in nature – the influence of protein-induced macrocycle distortion on the biological function of tetrapyrroles

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