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Kojima, Takahiko,Nakayama, Kazuya,Ikemura, Kenichiro,Ogura, Takashi,Fukuzumi, Shunichi American Chemical Society 2011 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.133 No.30
<P>A coordinatively saturated ruthenium(II) complex having tetradentate tris(2-pyridylmethyl)amine (TPA) and bidentate 2,2′-bipyridine (bpy), [Ru(TPA)(bpy)]<SUP>2+</SUP> (<B>1</B>), was oxidized by a Ce(IV) ion in H<SUB>2</SUB>O to afford a Ru(IV)-oxo complex, [Ru(O)(H<SUP>+</SUP>TPA)(bpy)]<SUP>3+</SUP> (<B>2</B>). The crystal structure of the Ru(IV)-oxo complex <B>2</B> was determined by X-ray crystallography. In <B>2</B>, the TPA ligand partially dissociates to be in a facial tridentate fashion and the uncoordinated pyridine moiety is protonated. The spin state of <B>2</B>, which showed paramagnetically shifted NMR signals in the range of 60 to −20 ppm, was determined to be an intermediate spin (<I>S</I> = 1) by the Evans’ method with <SUP>1</SUP>H NMR spectroscopy in acetone-<I>d</I><SUB>6</SUB>. The reaction of <B>2</B> with various oraganic substrates in acetonitrile at room temperature afforded oxidized and oxygenated products and a solvent-bound complex, [Ru(H<SUP>+</SUP>TPA)(bpy)(CH<SUB>3</SUB>CN)], which is intact in the presence of alcohols. The oxygenation reaction of saturated C–H bonds with <B>2</B> proceeds by two-step processes: the hydrogen abstraction with <B>2</B>, followed by the dissociation of the alcohol products from the oxygen-rebound complexes, Ru(III)-alkoxo complexes, which were successfully detected by ESI-MS spectrometry. The kinetic isotope effects in the first step for the reaction of dihydroanthrathene (DHA) and cumene with <B>2</B> were determined to be 49 and 12, respectively. The second-order rate constants of C–H oxygenation in the first step exhibited a linear correlation with bond dissociation energies of the C–H bond cleavage.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2011/jacsat.2011.133.issue-30/ja2037645/production/images/medium/ja-2011-037645_0013.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja2037645'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja2037645'>ACS Electronic Supporting Info</A></P>
Brown Tumor of the Patella Caused by Primary Hyperparathyroidism: A Case Report
Tomoko Irie,Taro Mawatari,Satoshi Ikemura,Gen Matsui,Takahiro Iguchi,Hiroaki Mitsuyasu 대한영상의학회 2015 Korean Journal of Radiology Vol.16 No.3
It has been reported that the common sites of brown tumors are the jaw, pelvis, ribs, femurs and clavicles. We report our experience in a case of brown tumor of the patella caused by primary hyperparathyroidism. An initial radiograph and CT showed an osteolytic lesion and MR images showed a mixed solid and multiloculated cystic tumor in the right patella. One month after the parathyroidectomy, rapid bone formation was observed on both radiographs and CT images.