Reactions of iminophosphanes with chlorotris(triphenylphosphine)rhodium(I): generation and NMR identification of the first iminophosphanerhodium(I) and iminophosphanerhodium(III) complexes

Iminophosphanes [RO-P=NAr] (R = Me, 2-MeC6H4; Ar = 2,4,6-Bu'3C6H2) 1a,b react with RhClL3 (L = Ph3P) via ligand exchange to give KP-iminophosphane complexes of rhodium(i) [RhCl(MeOP=NAr)2L] 2 and [PhCl(2-MeC6H4OP=NAr)L2] 3. Under analogous conditions, P-halogenoiminophosphanes [X-P=NAr] (X = Cl, Br, I) 3a–c undergo a facile oxidative addition of the P-X bond, forming five-coordinate iminophosphanerhodium(III) complexes of composition [L2Cl(X)Rh(σ-P=BAr)] 5

Radiation and the Risk of Chronic Lymphocytic and Other Leukemias among Chornobyl Cleanup Workers

Background: Risks of most types of leukemia from exposure to acute high doses of ionizing radiation are well known, but risks associated with protracted exposures, as well as associations between radiation and chronic lymphocytic leukemia (CLL), are not clear.
 Objectives: We estimated relative risks of CLL and non-CLL from protracted exposures to low-dose ionizing radiation.
 Methods: A nested case–control study was conducted in a cohort of 110,645 Ukrainian cleanup workers of the 1986 Chornobyl nuclear power plant accident. Cases of incident leukemia diagnosed in 1986–2006 were confirmed by a panel of expert hematologists/hematopathologists. Controls were matched to cases on place of residence and year of birth. We estimated individual bone marrow radiation doses by the Realistic Analytical Dose Reconstruction with Uncertainty Estimation (RADRUE) method. We then used a conditional logistic regression model to estimate excess relative risk of leukemia per gray (ERR/Gy) of radiation dose.
 Results: We found a significant linear dose response for all leukemia [137 cases, ERR/Gy = 1.26 (95% CI: 0.03, 3.58]. There were nonsignificant positive dose responses for both CLL and non-CLL (ERR/Gy = 0.76 and 1.87, respectively). In our primary analysis excluding 20 cases with direct in-person interviews less than 2 years from start of chemotherapy with an anomalous finding of ERR/Gy = –0.47 (95% CI: less than –0.47, 1.02), the ERR/Gy for the remaining 117 cases was 2.38 (95% CI: 0.49, 5.87). For CLL, the ERR/Gy was 2.58 (95% CI: 0.02, 8.43), and for non-CLL, ERR/Gy was 2.21 (95% CI: 0.05, 7.61). Altogether, 16% of leukemia cases (18% of CLL, 15% of non-CLL) were attributed to radiation exposure.
 Conclusions: Exposure to low doses and to low dose-rates of radiation from post-Chornobyl cleanup work was associated with a significant increase in risk of leukemia, which was statistically consistent with estimates for the Japanese atomic bomb survivors. Based on the primary analysis, we conclude that CLL and non-CLL are both radiosensitive.

Methylidynetrisphosphonates: Promising C1 building block for the design of phosphate mimetics

Methylidynetrisphosphonates are representatives of geminal polyphosphonates bearing three phosphonate (PO3H2) groups at the bridged carbon atom. Like well-known methylenebisphosphonates (BPs), they are characterized by a P–C–P backbone structure and are chemically stable mimetics of the endogenous metabolites, i.e., inorganic pyrophosphates (PPi). Because of its analogy to PPi and an ability to chelate metal ions, the 1,1,1-trisphosphonate structure is of great potential as a C1 building block for the design of phosphate mimetics. The purpose of this review is to present a concise summary of the state of the art in trisphosphonate chemistry with particular emphasis on the synthesis, structure, reactions, and potential medicinal applications of these compounds

Synthese und Strukturbestimmung von 1-Metallo-1,2-Dihydrophospheten (η5-C5Me5)(CO)2M-PCH(E)-C(E)=C-NMe2 (M = Fe, Ru; E = CO2Me, CN)

Weber L, Kaminski O, Stammler H-G, Neumann B, Romanenko VD. Synthese und Strukturbestimmung von 1-Metallo-1,2-Dihydrophospheten (η5-C5Me5)(CO)2M-PCH(E)-C(E)=C-NMe2 (M = Fe, Ru; E = CO2Me, CN). Zeitschrift für Naturforschung. B. 1993;48(12):1784-1794.The metallo-phosphaalkenes ([eta]5-C5Me5)(CO)2M-P=C(NR2)2 (4a,b,5) result from the reaction of the corresponding bromo compounds ([eta]5-C5Me5)(CO)2MBr with Me3Si-P=C(NR2)2. The complexes 4a and 5a are cleanly converted into the 1-metallo-1,2-dihydrophosphetes ([eta]5-C5Me5)(CO)2M-PCH(E)-C(E)=C-NMe2 (10 a-c) (M = Fe, Ru; E = CO2Me, CN) by treatment with equimolar amounts of dimethyl fumarate or fumarodinitrile, respectively. The products 4a, b, 5 and 10 a-c have been characterized by elemental analysis as well as by spectroscopic data (IR, 1H, 13C, 31P NMR, MS). The molecular structures of 4a and 10a have been determined by single crystal X-ray analysis

Mono- and Diaminocarbenes from Chloroiminium and -amidinium Salts:Synthesis of Metal-Free Bis(dimethylamino)carbene

2 páginas, 1 tabla, 3 esquemas.Bis(trimethylsilyl)mercury cleanly reacts at low temperature with chloroamidinium and -iminium chlorides, generating persistent metal-free cyclic and acyclic diaminocarbenes, as well as transient aryl-, chloro-, and hydrogenoaminocarbenes; with the latter, the corresponding olefin dimers were isolated, whereas with the former, no dimerization processes were observed.We are grateful to the ACS/PRF (38192-AC4) and RHODIA for financial support of this work, and to the Spanish Ministerio de Educacion, Cultura y Deporte, for a postdoctoral fellowship (S.C.)Peer reviewe

Crude Oil Market Functioning and Sustainable Development Goals: Case of OPEC++-Participating Countries

This article aims to substantiate the factors by which the oil industry influences the sustainable development of OPEC++-participating countries under conditions of uncertainty. The impact of the price parameters of the world oil market and the tools of its regulation on the sustainability of OPEC++-participating countries was assessed using panel regression analysis. The sustainable development level of OPEC++-participating countries was analyzed by the integrated estimation method, focusing on crude oil market functioning features. Undoubtedly, we can testify that there is a direct correlation between the country’s level of socio-economic development and sustainable development. In resource economies, a reduction in oil production and exports cannot have the same effect on sustainable development as in countries that do not produce oil, or are characterized by a higher level of economic development. With an appropriate level of economic diversification and the effectiveness of the institutional framework for managing the oil market, sustainable development can be achieved. Based on the model of the integrated assessment of the sustainable development of oil-exporting countries, the impact of statistically significant financial investors’ panic factor on the imbalance of oil prices due to the uncertainty of economic development was determined. Key indicators that create a panic factor in the oil market were identified. These include the indicators of the number of countries enforcing lockdown and the pandemic’s duration. We argue for the need to develop an effective strategy for achieving the sustainable development goals (SDGs) in OPEC++-participating countries, based on the management of crude oil supply and demand forces and by considering the effect of financial investors’ panic factor on the oil market