Reaktionen cyclischer Carbonsäureanhydride mit (α, α′‐Dipyridyl)‐(Cyclooctadien‐1, 5)‐nickel

Abstract

(dipy)Ni(COD) reagiert mit Maleinsäureanhydrid (MSA) unter Substitution zu (dipy)Ni(MSA)2 (I) und (dipy)Ni(MSA) (II). Während in I die Bindung nur über die C = C‐Gruppe erfolgt, Koordiniert MSA in II zusätzlich über eine Carbonylfunktion. Mit Phthalsäureanhydrid (PSA) und Bernsteinsäureanhydrid (BSA) ergibt (dipy)Ni(COD) im Zuge einer Redox‐addition Sechsgliedrige Metallacyclen V und VII, die bei erhöhter Temperatur unter Decarbonylierung in die fünfgliedrigen Metallacyclen VI bzw. VIII übergehen. Die IR‐Spektren der neuen Verbindungen werden diskutiert.

Nickelacyclic Carboxylates with Pyridine‐Based Ligand Sets – From Mononuclear Complexes to Supramolecular Architectures by Hydrogen Bonding

“…[4] Particularly interesting is their preparation by oxidative coupling of CO 2 and simple alkenes at the nickel centre, [5][6][7] which can be considered as the initial step of so far not realized catalytic reactions using CO 2 as a C1 building block. [8,9] Some of those complexes are valuable starting compounds in organic synthesis, for example for the preparation of carboxylic acids or their derivatives.…”

Dppm stabilized nickelacyclic carboxylates as building blocks of oligonuclear nickel complexes

“…Nickelacyclic carboxylates are a well-known group of compounds which have been synthesized by different synthetic approaches [1][2][3][4]. Their preparation by oxidative coupling of CO 2 and unsaturated hydrocarbons at the nickel centre [5-9], which can be considered as the initial step of catalytic reactions using CO 2 as C1 building block, is especially interesting [10][11][12][13].…”

“…When a stoichiometry close to the one, observed in the product 2, was applied a more complicated product mixture was obtained from which crystals of 2 were isolated by fractionized crystallization besides the starting material and [NiBr 2 (py) 4 …”

“…In presence of NiBr 2 , the related trinuclear complex [(l 2 -dppm){Ni(C 2 H 4 COO)} 2 Ã NiOH(H 2 O)(py) 2 ] + Br À (2) was isolated and characterized by elemental analysis, IR measurements and X-ray single crystal structural analysis. These compounds are rare examples of organonickel compounds with l 3 -hydroxide ligands and to best of our knowledge the first nickelacyclic carboxylates stabilized by such simple inorganic compounds as ligands.Ó 2010 Elsevier B.V. All rights reserved.Nickelacyclic carboxylates are a well-known group of compounds which have been synthesized by different synthetic approaches [1][2][3][4]. Their preparation by oxidative coupling of CO 2 and unsaturated hydrocarbons at the nickel centre [5-9], which can be considered as the initial step of catalytic reactions using CO 2 as C1 building block, is especially interesting [10][11][12][13].…”

A new set of nickelacyclic carboxylates (“nickelalactones”) containing pyridine as supporting ligand: synthesis, structures and application in C–C– and C–S– linkage reactions

“…Nickelacyclic carboxylates (''nickelalactones'') (Scheme 1) consisting of a Ni-C-C-COO-framework and N-N chelating ligands or phosphines as supporting ligands are well-known compounds which have been synthesized by different synthetic approaches [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. Of special interest is the oxidative coupling between carbon dioxide, unsaturated substrates and Ni(0) complexes which may open new ways for using CO 2 as building block in organic synthesis.…”