A terminal molybdenum carbide prepared by methylidyne deprotonation

The carbide anion [CMo{N(R)Ar}_3]– [R = C(CD_3)_2CH_3, Ar = C_6H_3Me_2-3,5], is obtained by deprotonation of the corresponding methylidyne compound, [HCMo{N(R)Ar}_3], and is characterized by X-ray diffraction as its {K(benzo-15-crown-5)_2}+ salt, thereby providing precedent for the carbon atom as a terminal substituent in transition-metal chemistry

The contribution of Chinese exports to climate change

Within 5 years, China's CO2 emissions have nearly doubled, and China may already be the world's largest emitter of CO2. Evidence suggests that exports could be a main cause for the rise in Chinese CO2 emissions; however, no systematic study has analyzed this issue, especially over time. We find that in 2005, around one-third of Chinese emissions (1700 Mt CO2) were due to production of exports, and this proportion has risen from 12% (230 Mt) in 1987 and only 21% (760 Mt) as recently as 2002. It is likely that consumption in the developed world is driving this trend. A majority of these emissions have largely escaped the scrutiny of arguments over “carbon leakage” due to the current, narrow definition of leakage. Climate policies which would make the developed world responsible for China's export emissions have both benefits and costs, and must be carefully designed to achieve political consensus and equity. Whoever is responsible for these emissions, China's rapidly expanding infrastructure and inefficient coal-powered electricity system need urgent attention

Metasomatic Reactions between Archean Dunite and Trondhjemite at the Seqi Olivine Mine in Greenland

A metasomatic zone formed between the contact of a 2940 ± 5 Ma intrusive trondhjemite sheet in the Archean dunite of the Seqi Ultramafic Complex, SW Greenland, consists of three distinct mineral zones dominated by (1) talc, (2) anthophyllite, and (3) phlogopite. These zones supposedly resulted from a process of dissolution of olivine by silica rich fluid residual from the trondhjemite magma, with crystallization of secondary minerals along a compositional gradient in the fluid phase. A zircon crystal inclusion in a large (4 cm) olivine porphyroblast was dated in situ via LA-ICP-MS U–Pb isotope analysis, yielding a weighted mean 207Pb/206Pb age of 2963 ± 1 Ma, which coincides with granulite facies metamorphism and potential dehydration. Considering phase relations appropriate for the dunite composition, we deduced the talc forming conditions to be at temperatures of 600–650 °C and at a pressure below 1 GPa. This is supported by oxygen isotope data for talc, anthophyllite and phlogopite in the metasomatic zone, which suggests formation in the temperature range of 600–700 °C from fluids that had a δ18O of ~8‰ and a Δ’17O0.528 of about −40 ppm, i.e., from fluids that could have been derived from the late stage trondhjemite sheet

Protecting growth options in dynamic markets: The role of strategic disclosure in integrated intellectual property strategies

Given recent developments in information technology and intellectual property (IP) legislation, technology firms may benefit from an integrated IP strategy that combines patenting with strategic disclosure. This article presents a series of cases that introduce various aspects of strategic disclosure and provide a framework for how and when such practices may be merited as part of an integrated IP strategy. To help CEOs decide on the economics and efficiency of the practice, practical guidelines are provided for when it might be a useful complement to the firm's other IP management practices

The drivers of Chinese CO2 emissions from 1980 to 2030

China's energy consumption doubled within the first 25 years of economic reforms initiated at the end of the 1970s, and doubled again in the past 5 years. It has resulted of a threefold CO2 emissions increase since early of 1980s. China's heavy reliance on coal will make it the largest emitter of CO2 in the world. By combining structural decomposition and input–output analysis we seek to assess the driving forces of China's CO2 emissions from 1980 to 2030. In our reference scenario, production-related CO2 emissions will increase another three times by 2030. Household consumption, capital investment and growth in exports will largely drive the increase in CO2 emissions. Efficiency gains will be partially offset the projected increases in consumption, but our scenarios show that this will not be sufficient if China's consumption patterns converge to current US levels. Relying on efficiency improvements alone will not stabilize China's future emissions. Our scenarios show that even extremely optimistic assumptions of widespread installation of carbon dioxide capture and storage will only slow the increase in CO2 emissions

Assembly of Molybdenum/Titanium μ-Oxo Complexes via Radical Alkoxide C−O Cleavage

Three-coordinate Ti(NRAr)_3 [R = C(CD_3)_2(CH_3), Ar = C_6H_3Me_2] was prepared in 73% yield by sodium amalgam reduction of ClTi(NRAr)_3 and in 83% yield upon treatment of TiCl_3(THF)_3 with 3 equiv of Li(NRAr)(OEt_2) in the presence of TMEDA. Ti(^tBuNPh)_3 was prepared similarly in 75% yield by treatment of TiCl_3(THF)_3 with 3 equiv of Li(^tBuNPh)(OEt_2) in the presence of TMEDA. Reaction of Ti(NRAr)_3 with NMo(O^tBu)_3 in hydrocarbon solvents at −35 °C generates a thermally unstable intermediate formulated as (^tBuO)_3Mo[μ-N]Ti(NRAr)_3, which readily loses a tert-butyl radical and isomerizes at 25 °C. Kinetics of the latter process were obtained over the temperature range 20−60 °C; the process exhibits clean first-order behavior. The following activation parameters were obtained:  ΔH⧧ = 21.4 ± 0.2 kcal mol^(-1) and ΔS⧧ = −3.7 ± 0.6 cal mol^(-1) K^(-1). The oxo-bridged product (^tBuO)_2(N)Mo[μ-O]Ti(NRAr)_3 was isolated in 83% yield from this reaction. Full characterization of the latter diamagnetic complex included an X-ray crystal structure and an ^(15)N NMR study. Ti(NRAr)_3 (1 equiv) reacts further with (^tBuO)_2(N)Mo[μ-O]Ti(NRAr)_3 to generate a species formulated as a second paramagnetic nitrido-bridged intermediate, (^tBuO)_2Mo{[μ-O]Ti(NRAr)_3}{[μ-N]Ti(NRAr)_3}, which at 25 °C loses a tert-butyl radical and isomerizes to give the final product, (^tBuO)(N)Mo{[μ-O]Ti(NRAr)_3}_2, isolated as an orange powder in 91% yield. Characterization of the latter diamagnetic complex included an ^(15)N NMR study. Attempts to displace a third tert-butyl radical by treatment of (^tBuO)(N)Mo{[μ-O]Ti(NRAr)_3}_2 with Ti(NRAr)_3 led to no reaction. Treatment of (^tBuO)(N)Mo{[μ-O]Ti(NRAr)_3}_2 with neat methyl iodide led to the isolation of (MeO)(N)Mo{[μ-O]Ti(NRAr)_3}_2 in 51% yield; ^(13)C and nitrido-^(15)N derivatives of this species were prepared for spectroscopic characterization. O_2Mo{[μ-O]Ti(^tBuNPh)_3}_2 was prepared in 59% yield upon treatment of MoO_2(O^tBu)_2 with 2 equiv of Ti(^tBuNPh)_3 in benzene at 65 °C. Full characterization of O_2Mo{[μ-O]Ti(^tBuNPh)_3}_2 included a single-crystal X-ray diffraction study. Previously reported (^iPrO)_3V[μ-O]Ti(NRAr)_3 was oxidized with ferrocenium triflate to give TfOTi(NRAr)_3 and OV(O^iPr)_3. TfOTi(NRAr)_3 was prepared independently in 80% yield by treatment of Ti(NRAr)_3 with ferrocenium triflate. (^iPrO)_3V[μ-O]Ti(NRAr)_3 is stable in the presence of methyl iodide. ITi(NRAr)_3 was prepared independently by treatment of Ti(NRAr)_3 with the stoichiometric amount of iodine. Paramagnetic (^tBuO)_3V[μ-O]Ti(NRAr)_3 was prepared as orange-brown needles in 94% yield and was found to be thermally stable. The relatively robust μ-nitrido compound (Me_2N)_3Mo[μ-N]Ti(^tBuNPh)_3, which was prepared in 77% isolated yield, showed no decomposition when heated in benzene at 70 °C for 13 h