Photofragmentation kinetics of some triruthenium carbonyl clusters

Binuclear Complexes of Ruthenium and Osmium Containing Metal Metal Bonds

“…45 Similar to its unprotonated parent, [Ru 2 (|i-H)(u-CO)(CO) 3 (u-etipdp) 2 ] + is coordinatively unsaturated and reacts spontaneously at ambient temperature with a wide range of nucleophiles including carbon monoxide, alkynes, sulfur, carbon disulfide, and hydride, halide, cyanide and hydrogensulfide ions. 50 The structure of the product of the iodide reaction, [Ru 2 (|i-I)H(|i sb -CO)(CC)) 2 (u-etipdp) 2 ] (43)* has been [Ru 2 H 2 (CO) 4 (|i-etipdp) 2 ] (48)*, the product o f the reaction involving dihydrogen and the tetraisopropoxydiphosphazane derivatives (3) or (36) and in which, as determined by x-ray crystallography, the hydrogens are situated equatorially and trans to each other on different ruthenium atoms, is also highly reactive, typically reductively eliminating dihydrogen i n its reactions with nucleophiles including alkynes. 39 …”

Reaction Intermediates in the Solution Photochemistry of a Tetrarhodium Carbonyl Cluster: FTIR Structural Characterization and Transient Kinetics

“…The mechanistic features of photochemical transformations occurring in these polynuclear complexes have been studied either by the matrix isolation technique [2][3][4][5] or by a photokinetic approach based on the treatment of quantum yield dependence on the concentration of reaction components. [6][7][8][9][10][11][12] These days, direct information about the chemical behavior of transient species formed after photoexcitation can be obtained by flash photolysis experiments. However, quantitative data of this sort are rarely found in the transition metal cluster literature.…”

“…This is particularly evident in their photochemical properties where most information has been obtained for simplest tri- and tetrametal clusters. The mechanistic features of photochemical transformations occurring in these polynuclear complexes have been studied either by the matrix isolation technique − or by a photokinetic approach based on the treatment of quantum yield dependence on the concentration of reaction components. − These days, direct information about the chemical behavior of transient species formed after photoexcitation can be obtained by flash photolysis experiments. However, quantitative data of this sort are rarely found in the transition metal cluster literature. ,, To some extent this lack of information about transient species formed after photoexcitation of the polynuclear complexes is due to the fact that the UV−vis probe techniques commonly used in flash photolysis experiments carry minimal structural information.…”

Synthesis and Structure of η4‐Enone Complexes of Ruthenium(0)

“…These transfer reagents were also used to trap unstable products [3] and for kinetic resolution of non-functionalized [Fe(C0),(v4-diene)] complexes [4] [5]. For the synthesis of [Fe(CO),(q4-enone)] complexes, previous methods included either thermal reaction by heating the enone and [Fe,(CO)J in toluene at 70'-80° [6] or irradiation of the enone and Fe(CO), in benzene [7]. The latter method usually yielded a mixture of the v2and y4-coordinated compounds.…”