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      HEXAMETHYLBENZENERUTHENIUM(II) COMPLEXES CONTAINING BIS(DIPHENYLPHOSPHINE)AMINE AND THEIR SULPHUR OR SELENIUM DERIVATIVES AS LIGANDS

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          Abstract

          Reaction of dinuclear complex [{(h6-C6Me6)Ru(µ-Cl)Cl} 2] with the ligand NH(PPh2)2 in 1:2 molar ratio affords the mononuclear complex [(h6-C6Me6)RuCl 2{h1-(PPh2)2NH}](1) which in turn reacts with AgPF6 to yield the cationic compound [(h6-C6Me6)RuCl{h 2-(PPh2)2NH}]PF6 (2). Complex 3 reacts with KOBut to give the neutral complex [(h6-C6Me6)RuCl{h 2-(PPh2)2N}](3). The anionic ligand of complex 3 reacts easily with HBF4 regenerating the starting complex and with MeI by N-methylation of the chelate ligand. The non coordinating P atom of complex 1 reacts with sulfur or selenium to form the P-coordinate monosulphide or selenide ligands, [{(h6-C6Me6)RuCl 2{h1PPh2NHP(E)Ph2 }] (5,6). The treatment of complexes 5 and 6 with AgPF6 affords cationic (7,8) or neutral (9,10) complexes depending of the solvent used. The neutral complex 9 can be N-derivatized by reaction with MeI

          Translated abstract

          La reacción del complejo dinuclear [{(h6-C6Me6)Ru(µ-Cl)Cl} 2] con el ligando NH(PPh2)2 en relación molar 1:2 genera el complejo mononuclear [(h6-C6Me6)RuCl 2{h1-(PPh2)2 NH}](1), el que posteriormente reacciona con AgPF6 formando el complejo catiónico [(h6-C6Me6)RuCl{h 2-(PPh2)2NH}]PF6 (2). El complejo 2 reacciona con KOBut con formación del complejo neutro [(h6-C6Me6)RuCl{h 2-(PPh2)2N}](3). El ligando aniónico del complejo 3 reacciona facilmente con HBF4 regenerando el complejo de partida y con MeI a través de la metilación del átomo de nitrógeno del ligando coordinado. El átomo de fósforo no coordinado del complejo 1 reacciona con azufre o selenio con formación del ligando coordinado monosustituído,[{(h6-C6 Me6)RuCl2{h1PPh 2NHP(E)Ph2}] (5,6). El tratamiento de los complejos 5 y 6 con AgPF6 conduce a la formación de compuestos catiónicos (7,8) o neutros (9,10) dependiendo del tipo de disolvente utilizado. El atomo de nitrógeno del complejo neutro 9 puede ser derivatizado por reacción con MeI

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          Most cited references 32

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          Metal-Organic Framework (MOF) Defects under Control: Insights into the Missing Linker Sites and Their Implication in the Reactivity of Zirconium-Based Frameworks.

          For three-dimensional (3D) metal-organic frameworks (MOFs), the presence and nature of structural defects has been recognized as a key factor shaping the material's physical and chemical behavior. In this work, the formation of the "missing linker" defects has been addressed in the model biphenyl-4,4'-dicarboxylate (bpdc)-based Zr MOF, UiO-67. The defect showed strong dependence on the nature of the modulator acid used in the MOF synthesis; the defects, in turn, were found to correlate with the MOF physical and chemical properties. The dynamic nature of the Zr6 (node)-monocarboxylate bond showed promise in defect functionalization and "healing", including the formation of X-ray-quality "defect-free" UiO-67 single crystals. Chemical transformations at defect sites have also been explored. The study was also extended to the isoreticular UiO-66 and UiO-68' systems.
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            Alkoxyboration Polymerization. Synthesis of Novel Poly(boronic carbamate)s

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              The electronic structure of inorganic benzenes: valence bond and ring-current descriptions.

              Valence bond (VB) theory and ring-current maps have been used to study the electronic structure of inorganic benzene analogues X(6)H(6) (X = C (1), Si (2)), X(6) (X = N (3), P (4)), X(3)Y(3)H(6) (X,Y = B,N (5), B,P (6), Al,N (7), Al,P (8)), and B(3)Y(3)H(3) (Y = O (9), S (10)). It is shown that the homonuclear compounds possess benzene-like character, with resonance between two Kekulé-like structures and induced diatropic ring currents. Heteronuclear compounds typically show localization of the lone pairs on the electronegative atoms; Kekulé-like structures do not contribute. Of the heteronuclear compounds, only B(3)P(3)H(6) (6) has some benzene-like features with a significant contribution of two Kekulé-like structures to its VB wave function, an appreciable resonance energy, and a discernible diatropic ring current in planar geometry. However, relaxation of 6 to the optimal nonplanar chair conformation is accompanied by the onset of localization of the ring current.
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                Author and article information

                Contributors
                Role: ND
                Role: ND
                Role: ND
                Role: ND
                Journal
                bscq
                Boletín de la Sociedad Chilena de Química
                Bol. Soc. Chil. Quím.
                Sociedad Chilena de Química (Concepción )
                0366-1644
                June 2000
                : 45
                : 2
                : 227-235
                Affiliations
                [1 ] Pontificia Universidad Católica de Chile Chile
                Article
                S0366-16442000000200009
                10.4067/S0366-16442000000200009
                c4441857-f179-46e7-a4fb-efde6466fa7b
                Product
                Product Information: website
                Categories
                CHEMISTRY, MULTIDISCIPLINARY

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