Photoassisted catalysis in organized media: olefin isomerization via photolysis of metal carbonyls in zeolites

Combined 1 H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

“…Ultimately, these findings show that the efficiency of a widely used IPC‐catalyzed isomerization reaction is solvent dependent. This study concerned one of the many possible IPC‐catalyzed isomerization reactions that may be studied …”

“…Iron pentacarbonyl (IPC) has been widely used in conjunction with ultraviolet (UV) light to catalyze a number of alkene isomerization reactions . The exact mechanisms for these reactions have been studied through computational, static, and ultrafast experimental techniques .…”

Reactions of aziridine, thiirane, and oxirane with isocyanide ligands in complexes of palladium(II) and platinum(II): syntheses of neutral five-membered cyclic diamino-, aminothio-, and aminooxycarbene compounds

“…6 The mono(isocyanide) complexes ds-Cl2(L)M(CNR) ( = Pd, Pt; 1-6; Table I) display values of = »( ) µ( -v-(N=C)free7 in the range 78-90 cm™1. For the bis(isocyanide) complexes rá-Cl2M(CNR)2 (M = Pd, Pt; [7][8][9][10][11][12]Table I) the Av shifts are in the range 81-109 cm™1. The positive Av values shown by [1][2][3][4][5][6][7][8][9][10][11][12] indicate that the isocyanide carbon is a potentially reactive electrophilic center8 toward nucleophiles to give carbene complexes.6 However, it has been noticed2 that a positive value of Av (>60 cm™1) appears to be a necessary but not sufficient condition for facilitating reactions of isocyanide ligands with nucleophiles.…”

“…For the bis(isocyanide) complexes rá-Cl2M(CNR)2 (M = Pd, Pt; [7][8][9][10][11][12]Table I) the Av shifts are in the range 81-109 cm™1. The positive Av values shown by [1][2][3][4][5][6][7][8][9][10][11][12] indicate that the isocyanide carbon is a potentially reactive electrophilic center8 toward nucleophiles to give carbene complexes.6 However, it has been noticed2 that a positive value of Av (>60 cm™1) appears to be a necessary but not sufficient condition for facilitating reactions of isocyanide ligands with nucleophiles. In order to test the influence of electronic and steric properties in the reactions of aziridine, thiirane, and oxirane with coordinated RNC ligands, we have examined as typical cases the behavior of aryl isocyanides such as p-MeOC6H4NC and p-MeC6H4NC (higher electron-withdrawing properties of the substituent R) and alkyl isocyanides such as f-BuNC and C6-HnNC (higher sterically demanding properties of the R group).…”

Inclusion of Organometallics in Zeolite Host Structures

“…Physisorption. Neutral metal carbonyls have been adsorbed in large-pore zeolites, primarily in faujasite-type structures [1,2]. We have recently shown that zeolite metal cations such as Na + provide weak binding sites for the carbonyl ligands [3].…”