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Reversible Pt^II-CH₃ deuteration without methane loss: metal-ligand cooperation vs. ligand-assisted Pt^II-protonation.

ABSTRACT: Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)Pt^II(CH₃)₂, reacts with CD₃OD at 25 °C to undergo complete deuteration of Pt-CH₃ fragments in ∼5 h without loss of methane to form (dpk)Pt^II(CD₃)₂ in virtually quantitative yield. The deuteration can be reversed by dissolution in CH₃OH or CD₃OH. Kinetic analysis and isotope effects, together with support from density functional theory calculations indicate a metal-ligand cooperative mechanism wherein DPK enables Pt-CH₃ deuteration by allowing non-rate-limiting protonation of Pt^II by CD₃OD. In contrast, other model di(2-pyridyl) ligands enable rate-limiting protonation of Pt^II, resulting in non-rate-limiting C-H(D) reductive coupling. Owing to its electron-poor nature, following complete deuteration, DPK can be dissociated from the Pt^II-centre, furnishing [(CD₃)₂Pt^II(μ-SMe₂)]₂ as the perdeutero analogue of [(CH₃)₂Pt^II(μ-SMe₂)]₂, a commonly used Pt^II-precursor.

SUBMITTER: Pal S

PROVIDER: S-EPMC8179389 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Greenhouse gas (GHG) emissions from Arctic permafrost soils create a positive feedback loop of climate warming and further GHG emissions. Active methane uptake in these soils can reduce the impact of GHG on future Arctic warming potential. Aerobic methane oxidizers are thought to be responsible for this apparent methane sink, though Arctic representatives of these organisms have resisted culturing efforts. Here, we first used in situ gas flux measurements and qPCR to identify relative methane sink hotspots at a high Arctic cytosol site, we then labeled the active microbiome in situ using DNA Stable Isotope Probing (SIP) with heavy 13CH4 (at 100 ppm and 1000 ppm). This was followed by amplicon and metagenome sequencing to identify active organisms involved in CH4 metabolism in these high Arctic cryosols. Sequencing of 13C-labeled pmoA genes demonstrated that type II methanotrophs (Methylocapsa) were overall the dominant active methane oxidizers in these mineral cryosols, while type I methanotrophs (Methylomarinovum) were only detected in the 100 ppm SIP treatment. From the SIP-13C-labeled DNA, we retrieved nine high to intermediate quality metagenome-assembled genomes (MAGs) belonging to the Proteobacteria, Gemmatimonadetes, and Chloroflexi, with three of these MAGs containing genes associated with methanotrophy. A novel Chloroflexi MAG contained a mmoX gene along with other methane oxidation pathway genes, identifying it as a potential uncultured methane oxidizer. This MAG also contained genes for copper import, synthesis of biopolymers, mercury detoxification, and ammonia uptake, indicating that this bacterium is strongly adapted to conditions in active layer permafrost and providing new insights into methane biogeochemical cycling. In addition, Betaproteobacterial MAGs were also identified as potential cross-feeders with methanotrophs in these Arctic cryosols. Overall, in situ SIP labeling combined with metagenomics and genome binning demonstrated to be a useful tool for discovering and characterizing novel organisms related to specific microbial functions or biogeochemical cycles of interest. Our findings reveal a unique and active Arctic cryosol microbial community potentially involved in CH4 cycling.

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Reversible PtII-CH3 deuteration without methane loss: metal-ligand cooperation vs. ligand-assisted PtII-protonation.

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Reversible Pt^II-CH₃ deuteration without methane loss: metal-ligand cooperation vs. ligand-assisted Pt^II-protonation.