Activation of a .beta.-lactone by oxidative addition and the structure of a platina(IV)lactone

Methyl–oxygen bond cleavage in hemilabile phosphine–ether ligand of ruthenium(II) complexes

“…The C-O bond cleavage reactions by transition-metal complexes that involve either strained systems or relatively weak C-O bonds, or systems driven by aromatization, are well known [2][3][4][5][6][7][8][9]. For example, C-O bond cleavage of strained cyclic ethers by transition-metals has been applied to catalysis of isomerization to carbonyl compounds, coupling to form esters, and carbonylation to lactones [2,6].…”

“…Another dealkylation pathway was suggested by the elimination of CH 3 Cl in the transition-metal halide complexes [16]. The reactivity of RuCl 2 (j 2 -Ph 2 PC 6 H 4 OMe-o) 2 (Ph 2 PC 6 H 4 OMe-o @ o-(diphenylphosphino)anisole) has been reported with CO and isocyanide to give mono and di-adducts, which do not perform dealkylation process [21,22].…”

Coupling of Epoxides to PtII‐Complexes with Carbon Dioxide and the Structure of a Cyclic Metallacarbonate

“…[12] All reactions for checking the diastereoselectivity were carried out directly in the NMR tube in deuterochloroform mixtures and for the preparative runs in dichloromethane. All reactions were complete within 24-48 h at room temperature, except for isoprene whose reaction was run in refluxing chloroform.…”

Acrylates from Alkenes and CO2, the Stuff That Dreams Are Made of

“…7c The catalytic carboxylation of unsaturated hydrocarbons with CO 2 to α,β-unsaturated carboxylates (i.e., acrylates) has been a topic of academic as well as industrial research for three decades, since seminal work of Hoberg 8 and Yamamoto 9 in the early 1980s. Although Hoberg et al reported the catalytic nickel-catalyzed reaction of alkenes and isocyanates (isoelectronic to CO 2 ) to acrylamides, 10 there has been no catalyst for the direct carboxylation of CO 2 and alkenes, neither based on nickel nor based on other metals from the nickel (Pd, Pt) [11][12][13][14][15][16][17][18][19][20] or iron triad, 21 titanium, 22 molybdenum, 23 tungsten, 24 zirconium, 25 or rhodium. 26 Basic obstacles for a catalytic transformation remained: (a) the endergonic nature of the overall reaction ΔG 0 R ¼ + 42:7 kJ=mol À Á , (b) the high activation barrier for the proposed β-hydride elimination from a nickelalactone or other Hoberg-type complexes (ΔG ¼ 164 kJ/mol), 27,28 and (c) the limitation to a small set of ligands paired with unproductively low reaction temperatures down to À70°C ( Fig.…”