Denis A. Kuznetsov

Climate Change During the Holocene (Past 12,000 Years)

This chapter summarises the climatic and environmental information that can be inferred from proxy archives over the past 12,000 years. The proxy archives from continental and lake sediments include pollen, insect remnants and isotopic data. Over the Holocene, the Baltic Sea area underwent major changes due to two interrelated factors—melting of the Fennoscandian ice sheet (causing interplay between global sea-level rise due to the meltwater and regional isostatic rebound of the earth’s crust causing a drop in relative sea level ) and changes in the orbital configuration of the Earth (triggering the glacial to interglacial transition and affecting incoming solar radiation and so controlling the regional energy balance). The Holocene climate history showed three stages of natural climate oscillations in the Baltic Sea region: short-term cold episodes related to deglaciation during a stable positive temperature trend (11,000–8000 cal year BP); a warm and stable climate with air temperature 1.0–3.5 °C above modern levels (8000–4500 cal year BP), a decreasing temperature trend; and increased climatic instability (last 5000–4500 years). The climatic variation during the Lateglacial and Holocene is reflected in the changing lake levels and vegetation , and in the formation of a complex hydrographical network that set the stage for the Medieval Warm Period and the Little Ice Age of the past millennium.

Tri-, tetra-, and hexanuclear mixed-valence molybdenum clusters: structural diversity and catalysis of acetylene hydrogenation

A series of novel cluster compounds comprising molybdenum in a low valence state was synthesized by means of a disproportionation of the dimeric compound [Mo+42Cl4(OCH3)4(CH3OH)2] (1). The reaction of 1 with CH3OH leads to the disproportionation of Mo+4 yielding an unusual mixed-valence cluster [Mo+3.54Cl4O2(OCH3)6(CH3OH)4] (2). By exploring this synthetic approach further, tri-{[Mo3Cl3(OCH3)7(CH3OH)3] (3)}, tetra-{[Mo4Cl4(OCH3)10(CH3OH)2] (4), [Mo4Cl3O(OCH3)9(CH3OH)3] (5), [Mo4Cl2(OCH3)12(CH3OH)2] (6)}, and hexanuclear {[Mo6Cl4O6(OCH3)10(CH3OH)2] (7)} molybdenum alkoxides were synthesized by the reaction of 1 with methanol and stoichiometric amounts of magnesium methoxide, thus providing a general facile access to the polynuclear methoxide complexes of a low-valence molybdenum. Due to the feasibility to adopt multiple oxidation states in a reversible manner and the documented competence of molybdenum alkoxide compounds to catalyze the reduction of inert molecules, including N2, the synthesized compounds were expected to function as catalysts of small molecule substrates reduction/hydrogenation. Accordingly, the reduction of acetylene (C2H2) to an ethylene (C2H4) and ethane (C2H6) mixture, in methanol (with water additives) serving as a reaction medium and a proton donor, and using sodium or europium amalgams as reducing agents, was performed in the presence of 2. Preliminary kinetic studies evidently point to a catalytic function of molybdenum species derived from 2, thus establishing the observed reactivity as a rare example of non-precious metal-catalyzed acetylene hydrogenation, providing, in addition, a convenient model for further mechanistic studies.

Synthesis, structure, and properties of polynuclear molybdenum(v,vi) oxomethoxides with magnesium

General conditions for the formation of heterometallic clusters by the simultaneous methanolysis of MoCl5 and MgCl2 were determined. The resultant alkalinity of the reaction solution, the Mg/Mo molar ratio, and the presence of traces of water are key factors responsible for the composition and structure of the mixed magnesium molybdenum methoxides that formed. The new decanuclear mixed-valence MoV,VI Mg oxomethoxide [MoV4O4(μ3-O)2(μ2-O)2MoVI2-O4(OMe)2Mg4(MeOH)6(μ3-OMe)6(μ2-OMe)8] (1) was synthesized by the reaction of lowernuclearity magnesium molybdenum oxoalkoxide complexes: NaMoV of the complex Na(MeOH)MoV2O2(μ2-OMe)3(OMe)4 (2) and MgMoVI of the complex [MoVIO2Mg(MeOH)2-(OMe)4]2 (3). The molecular structure of 1 was determined by X-ray diffraction.