Reactions of dioxoosmium(VI) porphyrins [Os(VI)(Por)O(2)] with excess 1,1-diphenylhydrazine in tetrahydrofuran at ca. 55 degrees C for 15 min afforded bis(hydrazido(1-))osmium(IV) porphyrins [Os(IV)(Por)(NHNPh(2))(2)] (1a, Por = TPP (meso-tetraphenylporphyrinato dianion); 1b, Por = TTP (meso-tetrakis(p-tolyl)porphyrinato dianion)), hydroxo(amido)osmium(IV) porphyrins [Os(IV)(Por)(NPh(2))(OH)] (2a, Por = TPP; 2b, Por = TTP), and bis(hydrazido(2-))osmium(VI) porphyrin [Os(VI)(Por)(NNPh(2))(2)] (3c, Por = TMP (meso-tetramesitylporphyrinato dianion)). The same reaction under harsher conditions (in refluxing tetrahydrofuran for ca. 1 h) gave a nitridoosmium(VI) porphyrin, [Os(VI)(Por)(N)(OH)] (4b, Por = TTP). Oxidation of 1a,b with bromine in dichloromethane afforded bis(hydrazido(2-)) complexes [Os(VI)(TPP)(NNPh(2))(2)] (3a) and [Os(VI)(TTP)(NNPh(2))(2)] (3b), respectively. All the new osmium porphyrins were identified by (1)H NMR, IR, and UV-vis spectroscopy and mass spectrometry; the structure of 2b was determined by X-ray crystallography (Os-NPh(2) = 1.944(6) A, Os-OH = 1.952(5) A).
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ic034389d | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Nitrite Reduction with HS/Thiol Mediated by Cobalt and Manganese Porphyrins in the Solid State.
Inorg Chem
January 2025
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States.
The endogenous reduction of nitrite to nitrosyl is drawing increasing attention as a protective mechanism against hypoxic injury in mammalian physiology and as an alternative source of NO, which is involved in a wide variety of biological activities. Thus, chemical mechanisms for this transformation, which are mediated by metallo proteins, are of considerable interest. The study described here examines the reactions of the biomimetic models Co(TTP)(NO) (TTP = meso-tetratolylporphyrinato dianion) and Mn(TPP)(ONO) (TPP = meso-tetraphenyl-porphyrinato dianion) in sublimated solid films with hydrogen sulfide (HS) and with ethanethiol (EtSH) at various temperatures from 77 K to room temperature using in situ infrared and optical spectroscopy.
View Article and Find Full Text PDFReproducibility and Repeatability of US Shear-Wave and Transient Elastography in Nonalcoholic Fatty Liver Disease.
Radiology
September 2024
From the Center for Ultrasound Research and Translation, Massachusetts General Hospital, 55 Fruit St, White Bldg, Rm 270, Boston, MA 02114 (T.T.P., A.O., X.W., Q.L., D.H., M.M., H.E., A.E.S.); Harvard Medical School, Boston, Mass (T.T.P., A.O., Q.L., A.E.S.); Pfizer, Cambridge, Mass (S.P.S.); Department of Radiology, University of Washington, Seattle, Wash (G.M.C.); Department of Ultrasound, Shenzhen University General Hospital, Shenzhen, China (Q.L.); Department of Radiology, Liver Imaging Group, University of California San Diego, La Jolla, Calif (M.S.M., Y.C., C.B.S., K.J.F.); MGH Fatty Liver Program, Gastrointestinal Unit, Massachusetts General Hospital, Boston, Mass (K.E.C.); BioAge Labs, Richmond, Calif (S.S.S.); Foundation for the National Institutes of Health, North Bethesda, Md (H.H., T.N.K.); Regeneron Pharmaceuticals, Tarrytown, NY (R.A.C.); Department of Medicine, Division of Gastroenterology, NAFLD Research Center, University of California at San Diego, La Jolla, Calif (R.L.); Quantitative Health Sciences, Cleveland Clinic Foundation, Cleveland, Ohio (N.A.O.); and Department of Internal Medicine, Division of Internal Medicine, Division of Gastroenterology, Virginia Commonwealth University Medical Center, Richmond, Va (A.J.S.).
Background US shear-wave elastography (SWE) and vibration-controlled transient elastography (VCTE) enable assessment of liver stiffness, an indicator of fibrosis severity. However, limited reproducibility data restrict their use in clinical trials. Purpose To estimate SWE and VCTE measurement variability in nonalcoholic fatty liver disease (NAFLD) within and across systems to support clinical trial diagnostic enrichment and clinical interpretation of longitudinal liver stiffness.
View Article and Find Full Text PDF[Thrombotic thrombocytopenic purpura, in a HIV-infected patient. Case report].
Rev Chilena Infectol
February 2021
Fundación Cardio-infantil, Bogotá, Colombia.
Hematological manifestations for human immunodeficiency virus (HIV) infection are frequent and diverse due to its ability to affect almost all cell lines. Among these, thrombotic thrombocytopenic purpura (TTP) is one of the thrombotic microangiopathies syndromes, characterized by the presence of thrombocytopenia and microangiopathic hemolytic anemia with impaired renal function. Nowadays, the relationship between these two entities is rare given the current highly active antiretroviral therapy (HAART).
View Article and Find Full Text PDFNitric Oxide Dioxygenation by O Adducts of Manganese Porphyrins.
Inorg Chem
December 2020
Department of Chemistry and Biochemistry, University of California, Santa Barbara, Santa Barbara, California 93106-9510, United States.
We describe here nitric oxide dioxygenation (NOD) by the dioxygen manganese porphyrin adducts Mn(Por)(η-O) (Por = the -tetra-phenyl or -tetra--tolylporphyrinato dianions, TPP and TTP). The Mn(Por)(η-O) was assembled by adding O to sublimed layers of Mn(Por). When NO was introduced and the temperature was slowly raised from 80 to 120 K, new IR bands with correlated intensities grew concomitant with depletion of the υ(O) band.
View Article and Find Full Text PDFLuminescent ruffled iridium(iii) porphyrin complexes containing N-heterocyclic carbene ligands: structures, spectroscopies and potent antitumor activities under dark and light irradiation conditions.
Chem Sci
January 2019
State Key Laboratory of Synthetic Chemistry , Institute of Molecular Functional Materials , HKU-CAS Joint Laboratory on New Materials and Department of Chemistry , The University of Hong Kong, Pokfulam Road , Hong Kong , China . Email:
A panel of iridium(iii) porphyrin complexes containing axial N-heterocyclic carbene (NHC) ligand(s) were synthesized and characterized. X-ray crystal structures of the bis-NHC complexes [Ir(ttp)(IMe)] (), [Ir(oep)(BIMe)] (), [Ir(oep)(I Pr)] () and [Ir(Ftpp)(IMe)] () display ruffled porphyrin rings with mesocarbon displacements of 0.483-0.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!