Recent developments in the chemistry of early transition metal porphyrin compounds

Brand, Holger; Arnold, John

doi:10.1016/0010-8545(94)01119-v

Cited by 114 publications

(69 citation statements)

References 223 publications

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“…Whereas dicarbonyl ligation in cis geometry has been invoked for early transition metal porphyrins, notably with Mo, it is definitely unexpected for the case of Fe or Co centers. 24,25 The reason is the difference in electronic structure and the atomic size that results in sizable displacements for Mo centers out of the porphyrin plane, eager to bind adducts in a multiple ligation mode.…”

Section: Identification Of Co Ligation Mode At Adsorbed Cotpp and Fetppmentioning

confidence: 99%

Cis-dicarbonyl binding at cobalt and iron porphyrins with saddle-shape conformation

et al. 2011

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Diatomic molecules attached to complexed Fe or Co centers are significant for many biological processes. In natural systems notably metallotetrapyrrole units carry respiratory gases or provide sensing and catalytic functions. Conceiving synthetic model systems strongly helped to rationalize the pertaining chemical foundations, whereby recent work highlights the importance of the prosthetic groups' conformational flexibility as an intricate variable affecting their functional properties.Here we present simple model systems to investigate at the single-molecule level the interaction of carbon monoxide with saddle-shaped Fe-and Co-porphyrin conformers, which have been stabilized as two-dimensional arrays on well-defined surfaces. Using scanning tunneling microscopy we identified a novel bonding scheme expressed in tilted monocarbonyl and cis-dicarbonyl configurations at the functional metalmacrocycle unit. Density functional theory modeling reveals that the weakly bonded diatomic carbonyl adduct can effectively bridge specific pyrrole groups with the metal atom because of the pronounced saddle-shape conformation of the porphyrin cage.

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Section: Identification Of Co Ligation Mode At Adsorbed Cotpp and Fetppmentioning

confidence: 99%

Cis-dicarbonyl binding at cobalt and iron porphyrins with saddle-shape conformation

et al. 2011

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“…[100] Amidophosphane-stabilized [14] zirconium complexes are highly suitable for the activation of nitrogen. The unusual characteristic here is the m-h 2 bonding mode of the N 2 ligand (side-on coordination).…”

Section: Reactions Of Complexed Dinitrogen With Hydrogenmentioning

confidence: 99%

Highlights in the Renaissance of Amidometal Chemistry

Kempe¹

2000

Angewandte Chemie International Edition

271

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Turning a disadvantage to an advantage: The rather disappointing reactivity of the metal - nitrogen bond in comparison to the metal - carbon bond resulted in the neglect of amidometal chemistry after its heyday at the end of the 1960s and beginning of the 1970s. Today it is precisely this disadvantage which is being applied through the use of amido ligands to produce inert complex fragments with well-defined reaction centers. In this way the chemistry of the early transition metals has been markedly enriched, and interesting alternatives to the classically regarded cyclopentadienyl ligands are now available.

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“…Dilithium porphyrin complexes have been shown to be valuable synthetic reagents for the preparation of a wide range of metalloporphyrins [1,2]. We recently reported [3] that the preparation of dilithium tetraarylporphyrins in diethyl ether results in a dilithium porphyrin bis(etherate) derivative with physical and chemical properties that differ from those of previously characterized tetrahydrofuran (THF) and dimethoxyethane (DME) adducts [4,5].…”

Section: Introductionmentioning

confidence: 93%

Ionic versus Covalent Bonding in Dilithium Porphyrins: X-ray Structure of Dilithium Tetraphenylporphyrin Bis(etherate)

Dawson

Arnold

1997

J. Porphyrins Phthalocyanines

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The solid state structure of dilithium tetraphenylporphyrin bis(etherate) has been determined by X-ray crystallography. The structure shows the lithium atoms are displaced out of the plane of the porphyrin, each coordinated in a square pyramidal fashion to the four nitrogen atoms in addition to a molecule of diethyl ether. The lithium atoms are identical, as required by the crystallographic inversion centre. X-ray data are as follows: [Formula: see text] (# 2) with a = 10.1908(4) Å, b = 11.6553(4) Å, c = 12.5199(5) Å, α = 111.644(1)°, β = 98.029(1)°, γ = 111.883(1)°, V = 1214.61(9)Å3, dcalc = 1.171 g cm -3 and Z = 1.

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Recent developments in the chemistry of early transition metal porphyrin compounds

Cited by 114 publications

References 223 publications

Cis-dicarbonyl binding at cobalt and iron porphyrins with saddle-shape conformation

Cis-dicarbonyl binding at cobalt and iron porphyrins with saddle-shape conformation

Highlights in the Renaissance of Amidometal Chemistry

Ionic versus Covalent Bonding in Dilithium Porphyrins: X-ray Structure of Dilithium Tetraphenylporphyrin Bis(etherate)

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