The title extended solid coordination compound, {[Fe(C(44)H(40)N(2)O(4)P(2))(C(3)H(7)NO)(2)](ClO(4))(2)·2C(3)H(7)NO}(n), was crystallized un-ex-pectedly from the reaction mixture containing the Trost ligand (1R,2R)-(+)-1,2-diamino-cyclo-hexane-N,N'-bis-(2'-di-phenyl-phosphinobenzo-yl) and Fe(ClO(4))(2)·6H(2)O in a 1:1 ratio in dimethyl-formamide (DMF) under reflux conditions. The polymeric complex is characterized by Fe(II) metal centers that are coordinated by two oxidized Trost ligands, each coordinated in a bidentate fashion in a square plane, along with two DMF mol-ecules above and below the plane [average Fe-O(DMF) = 2.086 (4) Å], forming an overall pseudo-octa-hedral geometry. The Trost ligand binds adjacent Fe(II) centers, each Fe(II) being bound through the O atom of one of the phosphine oxides [average Fe-O(PPh2) = 2.115 (4) Å] and the carbonyl O atom of the adjacent amide [average Fe-O(amide) = 2.192 (3) Å]. Disorder is observed in the co-solvated solvent: there are two DMF mol-ecules per Fe(II) centre, which were modeled as one DMF mol-ecule with complete occupancy and the other being modeled in two positions with equal occupancy. Disorder was also observed with one of the perchlorate anions, which was modeled in two positions with 0.75:0.25 occupancy.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2971940PMC
http://dx.doi.org/10.1107/S1600536809045188DOI Listing

Publication Analysis

Top Keywords

trost ligand
8
dmf mol-ecules
8
disorder observed
8
modeled positions
8
bis-perchlorate nn-dimethyl-formamide
4
nn-dimethyl-formamide disolvate]
4
disolvate] title
4
title extended
4
extended solid
4
solid coordination
4

Similar Publications

Interrupting Associative π-σ-π Isomerization Enables -Retentive Asymmetric Tsuji-Trost Reaction.

J Am Chem Soc

January 2025

New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.

The asymmetric Tsuji-Trost reaction has been extensively studied due to its importance in establishing stereogenic centers, often adjacent to an -olefin moiety in organic molecules. The generally preferential formation of chiral -olefin products is believed to result from the thermodynamically more stable -π-allylpalladium intermediate. The rapid associative π-σ-π isomerization makes it challenging to synthesize chiral -olefin products via the transient -π-allylpalladium intermediate.

View Article and Find Full Text PDF

Asymmetric Palladium Migration for Synthesis of Chiral-at-Cage o-Carboranes.

Angew Chem Int Ed Engl

October 2024

Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.

Metal migration strategy can offer BH functionalization of o-carboranes at different positions from where initial bond activation occurs to achieve bifunctionalized o-carboranes in one reaction. We report in this article an enantioselective 3,4-bifunctionalization of o-carboranes via asymmetric Pd migration with a high efficiency and up to 98 % ee. This asymmetric catalysis has a broad substrates scope, leading to the preparation of a class of chiral-at-cage o-carborane derivatives.

View Article and Find Full Text PDF

The Pd-catalysed decarboxylative asymmetric allylic alkylation (DAAA) has been applied to the enantioselective synthesis of sterically hindered benzofuran-3(2H)-one-derived α-aryl-β-keto esters employing the (R,R)-ANDEN phenyl Trost ligand. A range of substrates were synthesised, employing previously developed aryllead triacetate methodology to install various aryl groups. The resulting α-aryl-α-allyl benzofuran-3(2H)-one DAAA products were obtained in moderate to high yields and in enantioselectivities of up to 96 % ee, with the best results observed for substrates containing a di-ortho-substitution pattern on the aryl ring as well as naphthyl-containing substrates.

View Article and Find Full Text PDF

Stability-based approaches in chemoproteomics.

Expert Rev Mol Med

April 2024

Laboratory for Biomedical Mass Spectrometry, Biosciences Institute, Newcastle University, Newcastle-upon-Tyne, NE2 4HH, UK.

Target deconvolution can help understand how compounds exert therapeutic effects and can accelerate drug discovery by helping optimise safety and efficacy, revealing mechanisms of action, anticipate off-target effects and identifying opportunities for therapeutic expansion. Chemoproteomics, a combination of chemical biology with mass spectrometry has transformed target deconvolution. This review discusses modification-free chemoproteomic approaches that leverage the change in protein thermodynamics induced by small molecule ligand binding.

View Article and Find Full Text PDF

Enantioselective Ring-Closing Aminomethylamination of Allylic Aminodienes with Aminals Triggered by C-N Bond Metathesis.

Org Lett

March 2024

Key Laboratory of Precision and Intelligent Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China.

A conceptually novel strategy utilizing a cyclopalladated complex as an electrophile to activate the C-N bond for the C-N bond metathesis between allylamines and aminals is developed, which enables an efficient ring-closing aminomethylamination of allylic aminodienes and aminals. The reaction proceeds under mild reaction conditions and displays a remarkable scope. Utilizing a modified Trost-type diphosphine as the ligand, this method enables the efficient synthesis of 5-10-membered aminoallylated chiral -heterocycles in good yields with high enantiomeric excess values.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!