Oxidative addition of CO2 to the reduced Zr/Co complex (THF)Zr(MesNP(i)Pr2)3Co (1) followed by one-electron reduction leads to formation of an unusual terminal Zr-oxo anion [2][Na(THF)3] in low yield. To facilitate further study of this compound, an alternative high-yielding synthetic route has been devised. First, 1 is treated with CO to form (THF)Zr(MesNP(i)Pr2)3Co(CO) (3); then, addition of H2O to 3 leads to the Zr-hydroxide complex (HO)Zr(MesNP(i)Pr2)3Co(CO) (4). Deprotonation of 4 with Li(N(SiMe3)2) leads to the anionic Zr-oxo species [2][Li(THF)3] or [2][Li(12-c-4)] in the absence or presence of 12-crown-4, respectively. The coordination sphere of the Li(+) countercation is shown to lead to interesting structural differences between these two species. The anionic oxo fragment in complex [2][Li(12-c-4)] reacts with electrophiles such as MeOTf and Me3SiOTf to generate (MeO)Zr(MesNP(i)Pr2)3Co(CO) (5) and (Me3SiO)Zr(MesNP(i)Pr2)3Co(CO) (6), respectively, and addition of acetic anhydride generates (AcO)Zr(MesNP(i)Pr2)3Co(CO) (7). Complex [2][Li(12-c-4)] is also shown to bind CO2 to form a monoanionic Zr-carbonate, [(12-crown-4)Li][(κ(2)-CO3)Zr(MesNP(i)Pr2)3Co(CO)] ([8][Li(12-c-4)]). A more stable version of this compound [8][K(18-c-6)] is formed when a K(+) counteranion and 18-crown-6 are used. Binding of CO2 to [2][Li(12-c-4)] is shown to be reversible using isotopic labeling studies. In an effort to address methods by which these CO2-derived products could be turned over in a catalytic cycle, it is shown that the Zr-OMe bond in 5 can be cleaved using H(+) and the CO ligand can be released from Co under photolytic conditions in the presence of I2.
This research output has an Altmetric Attention Score of 2. This is our high-level measure of the quality and quantity of online attention that it has received. This Attention Score, as well as the ranking and number of research outputs shown below, was calculated when the research output was last mentioned on 14 March 2013.
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