Photoinduced declusterification of nonacarbonyl(.mu.3-methylidyne)tricobalt, nonacarbonyl(.mu.3-ethylidyne)tricobalt, and tricarbonylhydro(tri-.mu.-carbonylhexacarbonyltricobalt)iron

Abstract

Irradiation of solutions of HCCo3(CO)9 under an H2 atmosphere with visible or UV light leads to quantitative formation of Co4(CO)12 and production of methane. Under a 3:1 H2/CO atmosphere irradiation produces Co2(CO)8 with a 366-nm quantum yield of 0.03. Photolysis in the presence of D2 has shown that the methane derives from the apical CH group and not from CO. Irradiation of HCCo3(CO)9 in the presence of H2 and 1-hexene leads to catalytic isomerization to errand í/ww-2-hexene. The photochemical properties of CH3CCo3(CO)9 parallel those of HCCo3(CO)9, except that no reaction is observed under an H2/CO atmosphere. Irradiation of HFeCo3(CO)u and HFeCo3(CO)10(PPh3)2 in degassed solutions also leads to declusterification with subsequent formation of.Co4(CO)i2 and Co2(CO)6(PPh3)2, respectively.

Alkyne-substituted homo- and heterometallic carbonyl clusters of the iron, cobalt and nickel triads

“…Finally, it has been reported that treatment of Co3-(CO)9CMe with hydrogen, under light, affords ethane. 283 Similarly, it has been found that when H3Ru3-(CO)9C.CH2Bu-£ is treated with hydrogen,47 neohexane is obtained.…”

Hydroformylation of Alkylidyne(nonacarbonyl)tricobalt Clusters: Model Reaction for the Direct Conversion of Synthesis Gas into C1‐ and C2‐Oxygenated Compounds

“…The methoxy derivative (2). whose IR spectrum in the CO stretching region is superimposable on that of (I), reacted completely with CO/H2 (xylene, CO~(CO)~, ca.…”

“…Reaction of (2)-(4) and (6) with syngas: (2): The reaction was complete after 15 h at 120 C and ca. 115 bar syngas.…”

Photochemistry of Metal—Metal—Bonded Transition Element Complexes

“…Cleavage in the sense suggesLed by equation (23) can seemingly occur, though, since photoreactiort according to equation (24) has been observed (63).…”

“…Photolysis of the complex RCCo0(CO),Y (R -1, CH 3 ) under an H 2 atmosphere has been reported to yield declusterification with low quantum efficiency (63).…”