1995
DOI: 10.1021/ic00129a016
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Photochemistry of the Clusters Os3(CO)10(L) (L = 2,2'-Bipyridine, 2,2'-Bipyrimidine, 2,3-Dipyrid-2-ylpyrazine, 2,3-Dipyrid-2-ylbenzoquinoxaline). Reversible Opening of an Os-Os Bond with Formation of a Zwitterion

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Cited by 26 publications
(29 citation statements)
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“…[1][2][3] In comparison with σN,σNЈ-chelated 2,2Ј-bipyridine, its aromatic phosphorus derivative 4,4Ј,5,5Ј-tetramethyl-2,2Ј-biphosphinine (tmbp) binds as a fairly strong π-acceptor ligand in a variety of mononuclear complexes, and better stabilizes low oxidation states of the metal in the M(σP,σPЈ-tmbp) chelate ring. Such ligands include 4,4Ј-di-R-2,2Јbipyridine and pyridine-2-carbaldehyde-NЈ-R-imine (R ϭ alkyl).…”
Section: Introductionmentioning
confidence: 99%
“…[1][2][3] In comparison with σN,σNЈ-chelated 2,2Ј-bipyridine, its aromatic phosphorus derivative 4,4Ј,5,5Ј-tetramethyl-2,2Ј-biphosphinine (tmbp) binds as a fairly strong π-acceptor ligand in a variety of mononuclear complexes, and better stabilizes low oxidation states of the metal in the M(σP,σPЈ-tmbp) chelate ring. Such ligands include 4,4Ј-di-R-2,2Јbipyridine and pyridine-2-carbaldehyde-NЈ-R-imine (R ϭ alkyl).…”
Section: Introductionmentioning
confidence: 99%
“…The corresponding electronic transition exhibits negligible solvatochromism, [9] in contrast to the lowest-energy electronic transition of [Os 3 (CO) 10 (bpy)], which possesses a dominant metal(core)-to-ligand charge transfer character. [1,10] The involved frontier orbitals of 1 probably have a dominant contribution from the tmbp ligand. [8] This may explain the observed inherent photostability of 1, as no specific metal-ligand or metal-metal bonds are significantly weakened upon visible excitation.…”
Section: Resultsmentioning
confidence: 99%
“…Such ligands include 4,4Ј-di-R-2,2Ј-bipyridine and pyridine-2-carbaldehyde-NЈ-R-imine (R ϭ alkyl). [1][2][3] In comparison with σN,σNЈ-chelated 2,2Ј-bipyridine, its aromatic phosphorus derivative 4,4Ј,5,5Ј-tetramethyl-2,2Ј-biphosphinine (tmbp) binds as a fairly strong π-acceptor ligand in a variety of mononuclear complexes, and better stabilizes low oxidation states of the metal in the M(σP,σPЈ-tmbp) chelate ring. [4,5] In addition, it may bind as a cyclophosphahexatriene with localized double bonds, for example in [Mn 2 (CO) 6 (tmbp)] where it chelates to one Mn(CO) 3 moiety through the P lone pairs and to the other metal centre through the internal PϭC bonds.…”
Section: Introductionmentioning
confidence: 99%
“…Pure 2 was obtained as a purple powder in 85 % yield. 1 Crystallography: Crystal data and details of the structure determination of cluster 2 are presented in Table 9. Crystals of 2 ¥ C 6 H 12 were grown by heating a solution of the complex in cyclohexane for five days at 80 8C.…”
Section: Redox Behavior Of Clusters 1 Andmentioning
confidence: 99%
“…ÀOs(CO) 4 ÀOs (CO) 2 (a-diimine .À )]. [1,2] Electrochemical reduction of [Os 3 (CO) 10 (a-diimine)] initially gives the radical anions [Os 3 (CO) 10 (a-diimine .À )], which are thermally unstable and convert to various anionic open-triangle products in a series of chemical and electron-transfer steps. [3,4] In both the biradical photoproducts and the radical anions there is an unpaired electron localized on the reducible a-diimine ligand.…”
mentioning
confidence: 99%