Flash photolysis experiments have been carried out at ambient temperature to probe potential reaction intermediates in the carbonylation of the methylmanganese complex CH3Mn(CO)5 (M) togivetheacyl product CH3C(O)Mn(CO)5 (A). Photo-decarbonylation of A gives a long-lived transient C, whose time-resolved infrared spectrum shows but modest sensitivity to the coordinating ability of the solvent such as cyclohexane, perfluoromethylcyclohexane, tetrahydrofuran, and 2,5-dimethyl-THF. Notably, C has an unexpectedly long lifetime (exceeding milliseconds) in each of the solvents investigated. Kinetics studies in cyclohexane show the competing trapping by CO to re-form A and isomerization to M occurs with the respective rate constants kco = 3.8 × 103 M−1 s−1 and 10 s−1. The former value is 3 orders of magnitude less than expected for a solvento complex under these conditions. Thus, it is concluded that TRIR spectra and reactivity patterns of C reflect stabilization of this intermediate by η2-coordination of the acyl group. © 1993, American Chemical Society. All rights reserved.

Alkenones are biomarkers produced solely by algae in the order Isochrysidales that have been used to reconstruct sea surface temperature (SST) since the 1980s. However, alkenone-based SST reconstructions in the northern high latitude oceans show significant bias towards warmer temperatures in core-tops, diverge from other SST proxies in down core records, and are often accompanied by anomalously high relative abundance of the C37 tetra-unsaturated methyl alkenone (%C37:4). Elevated %C37:4 is widely interpreted as an indicator of low sea surface salinity from polar water masses, but its biological source has thus far remained elusive. Here we identify a lineage of Isochrysidales that is responsible for elevated C37:4 methyl alkenone in the northern high latitude oceans through next-generation sequencing and lab-culture experiments. This Isochrysidales lineage co-occurs widely with sea ice in marine environments and is distinct from other known marine alkenone-producers, namely Emiliania huxleyi and Gephyrocapsa oceanica. More importantly, the %C37:4 in seawater filtered particulate organic matter and surface sediments is significantly correlated with annual mean sea ice concentrations. In sediment cores from the Svalbard region, the %C37:4 concentration aligns with the Greenland temperature record and other qualitative regional sea ice records spanning the past 14 kyrs, reflecting sea ice concentrations quantitatively. Our findings imply that %C37:4 is a powerful proxy for reconstructing sea ice conditions in the high latitude oceans on thousand- and, potentially, on million-year timescales.