Reactions of the metal-metal triple bond in Cp2Mo2(CO)4 and related complexes
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Cited by (105)
Activity of Mo-Mo and Mo-P multiple bonds at the phosphinidene complex [Mo<inf>2</inf>Cp<inf>2</inf>{μ-P(2,4,6-C<inf>6</inf>H<inf>2</inf><sup>t</sup>Bu<inf>3</inf>)}(μ-CO)<inf>2</inf>] in reactions with isocyanides and phosphine ligands
2015, Inorganica Chimica ActaCitation Excerpt :The high unsaturation at the dimetal center in intermediate E might then trigger the oxidative addition of the P–H bond of the PHR∗ group to give a hydride-phosphinidene derivative F, as occurring in the 32-electron cation [Mo2Cp2(μ-PHR∗)(CO)4]+ [37]. Under photochemical conditions, however, the PR∗ group at intermediate F might still rearrange via intramolecular C–H cleavage of an ortho tBu group to give a hydride-phosphaindanide derivative, as observed in the photolysis of [Mo2Cp2(μ-PR∗)(CO)4] to give the hydride [Mo2Cp2(μ-H){μ-P(CH2CMe2)C6H2tBu2}(CO)4] under certain conditions [8,9]. In the case of intermediate F, this rearrangement would now render a dihydride intermediate G easily evolving H2 to yield the final products 9.
Cyclopentadienyl and related complexes of the group 6 elements having metal-metal triple bonds: Synthesis, structure, bonding and reactivity
2013, Coordination Chemistry ReviewsCitation Excerpt :This type of reaction often requires thermal or photochemical activation of the saturated precursor and has been also a general route to access compounds with M–M triple bonds. Benzene solutions of the chromium dimer [Cr2Cp*2(CO)6] yielded the 30-electron chromium complex [Cr2Cp*2(CO)4] upon heating above 40 °C or exposure to sunlight (Scheme 1, top) [9], and the dimers [M2Cp2(CO)4] (M = Mo, W) could be analogously prepared from the corresponding hexacarbonyl precursors via thermal activation in refluxing diglyme for 1.5–3 h with a N2 purge (Scheme 1, bottom) [10], but this procedure gave only a modest yield (23%) of the related tungsten dimer [W2{η5-C5H4(CO2Et)}2(CO)4] [11], this requiring heating of the corresponding hexacarbonyl precursor at 140 °C for 9 h in diglyme. Decarbonylation could be also induced on the molybdenum complex [Mo2{η5-C5(CH2Ph)5}2(CO)6] having a bulkier hydrocarbyl ligand (overnight reflux in toluene) to give [Mo2{η5-C5(CH2Ph)5}2(CO)4] in very good yields [12].