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mer, fac, and Bidentate Coordination of an Alkyl-POP Ligand in the Chemistry of Nonclassical Osmium Hydrides.

Inorganic Chemistry 2017 January 4
Nonclassical and classical osmium polyhydrides containing the diphosphine 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant(Pi Pr2 )2 ), coordinated in κ3 -mer, κ3 -fac, and κ2 -P,P fashions, have been isolated during the cyclic formation of H2 by means of the sequential addition of H+ and H- or H- and H+ to the classical trihydride OsH3 Cl{xant(Pi Pr2 )2 } (1). This complex adds H+ to form the compressed dihydride dihydrogen complex [OsCl(H···H)(η2 -H2 ){xant(Pi Pr2 )2 }]+ (2). Under argon, cation 2 loses H2 and the resulting unsaturated fragment dimerizes to give [(Os(H···H){xant(Pi Pr2 )2 })2 (μ-Cl)2 ]2+ (3). During the transformation the phosphine changes its coordination mode from mer to fac. The benzofuran counterpart of 1, OsH3 Cl{dbf(Pi Pr2 )2 } (4; dbf(Pi Pr2 )2 = 4,6-bis(diisopropylphosphino)dibenzofuran), also adds H+ to afford the benzofuran counterpart of 2, [OsCl(H···H)(η2 -H2 ){xant(Pi Pr2 )2 }]+ (5), which in contrast to the latter is stable and does not dimerize. Acetonitrile breaks the chloride bridge of 3 to form the dihydrogen [OsCl(η2 -H2 )(CH3 CN){xant(Pi Pr2 )2 }]+ (6), regenerating the mer coordination of the diphosphine. The hydride ion also breaks the chloride bridge of 3. The addition of KH to 3 leads to 1, closing a cycle for the formation of H2 . Complex 1 reacts with a second hydride ion to give OsH4 {xant(Pi Pr2 )2 } (7) as consequence of the displacement of the chloride. Similarly to the latter, the oxygen atom of the mer-coordinated diphosphine of 7 has a tendency to be displaced by the hydride ion. Thus, the addition of KH to 7 yields [OsH5 {xant(Pi Pr2 )2 }]- (8), containing a κ2 -P,P-diphosphine. Complex 8 is easily protonated to afford OsH6 {xant(Pi Pr2 )2 } (9), which releases H2 to regenerate 7, closing a second cycle for the formation of molecular hydrogen.

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