Irreversible Reduction of Dioxygen by Simple Peralkylated Diamine−Copper(I) Complexes:  Characterization and Thermal Stability of a [Cu2(μ-O)2]2+ Core

Mahadevan, Viswanath; Hou, Zhiguo; Cole, Adam P.; Root, David E.; Lal, Tapan K.; Solomon, Edward I.; Stack, T. Daniel P.

doi:10.1021/ja972946n

Cited by 209 publications

(204 citation statements)

References 22 publications

Supporting

Mentioning

191

Contrasting

Order By: Relevance

“…As has been shown by Stack et al, bidentate N-donor ligands are also capable of forming complexes containing the heterocyclic Cu 2 O 2 core portion. [4,16,17] The associated square-planar CuO 2 N 2 coordination sites are expected to be more accessible for external substrates that may act as targets for catalytic oxygenation reactions. [18][19][20] Following this approach, peralkylated diamine ligands have been used to stabilise either the bis(µ-oxo)dicopper() (Ocore complexes) or the µ-η 2 :η 2 -peroxodicopper() core portion (P-core complexes) depending on the type of substituents.…”

Section: Introductionmentioning

confidence: 99%

“…Although the O-core has yet not been detected in enzymatic systems, its relevance for hydroxylation activity seems likely because the equilibria between P-and O-core states proven for model complexes have to be taken into account. [3,16,[21][22][23] In our search for bifunctional N-donor ligands able to stabilise unusually high metal oxidation states we extended our interest towards guanidine-type systems. Following this approach, bis(tetramethylguanidino)propane (btmgp) was synthesised as the first member of a series of bifunctional peralkylated guanidine ligands designed for use in biomimetic coordination chemistry.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Tuning of Copper(I)–Dioxygen Reactivity by Bis(guanidine) Ligands

2005

View full text Add to dashboard Cite

A series of bis(guanidine) ligands designed for use in biomimetic coordination chemistry, namely bis(tetramethylguanidino)‐, bis(dipiperidinoguanidino)‐, and bis(dimethylpropyleno)propane (btmgp, DPipG2p and DMPG2p, respectively), has been extended to include bis(dimethylethyleneguanidino)propane (DMEG2p), which has both Namine atoms of each guanidine functionality connected by a short ethylene bridge, as a member. From this series, a family of novel bis(guanidine)copper(I) compounds – [Cu2(btmgp)2][PF6]2 (1), [Cu2(DPipG2p)2][PF6]2 (2), [Cu2(DMPG2p)2][PF6]2 (3), and [Cu2(DMEG2p)2][PF6]2·2MeCN (4) – has been synthesised. Single‐crystal X‐ray analysis of 1–4 demonstrated that these compounds contain dinuclear complex cations that contain twelve‐membered heterocyclic Cu2N4C6 rings with the Cu atoms being more than 4 Å apart. Each copper atom is surrounded by a set of two N‐donor functions from different ligands, resulting in linear N–Cu–N coordination sites. Depending on their individual substitution patterns, the guanidine moieties deviate from planarity by characteristic propeller‐like twists of the amino groups around their N–Cimine bonds. The influence of these groups on the reactivity of the corresponding complexes 1–4 with dioxygen was investigated at low temperatures by means of UV/Vis spectroscopy. The reaction products can be classified into μ‐η2:η2‐peroxodicopper(II) or bis(μ‐oxo)dicopper(III) complex cations that contain the {Cu2O2}2+ core portion as different isomers. The electronic properties of the specific bis(guanidine) ligands are discussed from the viewpoint of their σ‐donor and π‐acceptor capabilities, and it is shown that μ‐η2:η2‐peroxodicopper(II) complexes are stabilised relative to the bis(μ‐oxo)dicopper(III) ones if π conjugation within the guanidine moieties is optimised. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tuning of Copper(I)–Dioxygen Reactivity by Bis(guanidine) Ligands

2005

View full text Add to dashboard Cite

show abstract

“…[27][28][29][30][31] These Cu complexes (B and C) Scheme 2. Cu-catalyzed enantioselective hetero-coupling reaction for DM-NOBIN.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric catalysis of homo‐coupling of 3‐substituted naphthylamine and hetero‐coupling with 3‐substituted naphthol leading to 3,3′‐dimethyl‐2,2′‐diaminobinaphthyl and ‐2‐amino‐2′‐hydroxybinaphthyl

Yusa¹,

Kaito²,

Akiyama³

et al. 2009

Chirality

View full text Add to dashboard Cite

show abstract

“…Short metal-metal distances have been reported for Mn---Mn [147][148][149][150][151][152], for Fe---Fe [153][154][155], and for Cu---Cu [156][157][158][159][160]. Three moxo bridges (Scheme 12e) shorten the Mn---Mn distance [161].…”

mentioning

confidence: 99%

Orbitals in Inorganic Chemistry: Metal Rings and Clusters, Hydronitrogens, and Heterocyles

Inagaki

2009

Orbitals in Chemistry

View full text Add to dashboard Cite

A chemical orbital theory is useful in inorganic chemistry. Some applications are described for understanding and designing of inorganic molecules. Among the topics included are: (1) valence electron rules to predict stabilities of three- and four-membered ring metals and for those of regular octahedral M(6) metal clusters solely by counting the number of valence electrons; (2) pentagon stability (stability of five- relative to six-membered rings in some classes of molecules), predicted and applied for understanding and designing saturated molecules of group XV elements; (3) properties of unsaturated hydronitrogens N( m )H( n ) in contrast to those of hydrocarbons C( m )H( n ); (4) unusually short nonbonded distances between metal atoms in cyclic molecules.

show abstract

Irreversible Reduction of Dioxygen by Simple Peralkylated Diamine−Copper(I) Complexes: Characterization and Thermal Stability of a [Cu₂(μ-O)₂]²⁺ Core

Cited by 209 publications

References 22 publications

Tuning of Copper(I)–Dioxygen Reactivity by Bis(guanidine) Ligands

Tuning of Copper(I)–Dioxygen Reactivity by Bis(guanidine) Ligands

Asymmetric catalysis of homo‐coupling of 3‐substituted naphthylamine and hetero‐coupling with 3‐substituted naphthol leading to 3,3′‐dimethyl‐2,2′‐diaminobinaphthyl and ‐2‐amino‐2′‐hydroxybinaphthyl

Orbitals in Inorganic Chemistry: Metal Rings and Clusters, Hydronitrogens, and Heterocyles

Contact Info

Product

Resources

About