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Trapping of a 12-Valence-Electron Osmium Intermediate

机译:诱捕12价电子O中间体

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摘要

The hydride-dihydrogen complex [OsH(eta(2)-H-2){kappa N-3,C,C-CH2 = CH-o-C5H4N}((PPr3)-Pr-i)(2)]BF4 (1) is a "functional equivalent" of the 12-valence-electron monohydride cation "[OsH((PPr3)-Pr-i)(2)](+)", which is trapped by aromatic solvents, such as toluene, benzene, and fluorobenzene to form the arene derivatives [OsH(eta(6)-C6H5R)((PPr3)-Pr-1)(2)]BF4 (R = CH3 (2), H (3). F(4)). This "functional equivalent" can be also generated by protonation of the hexahydride OsH6(-)((PPr3)-Pr-i)(2)(5) with 1 equiv of HBF4 and subsequent release of three hydrogen molecules. The monohydride is also trapped by 5. The protonation of the latter with 0.5 equiv of HBF4 yields the heptahydride dimer [{OsH2((PPr3)-Pr-i)(2)}(2)(mu-H)(3)]BF4 (6). which does not undergo exchange of bridging and terminal hydrdes.
机译:氢化物-二氢络合物[OsH(eta(2)-H-2){κN-3,C,C-CH2 = CH-o-C5H4N}(((PPr3)-Pr-i)(2)] BF4( 1)是十二价电子一氢化物阳离子“ [OsH((PPr3)-Pr-i)(2)](+)”的“功能当量”,它被芳族溶剂(例如甲苯,苯)捕获,和氟苯形成芳烃衍生物[OsH(eta(6)-C6H5R)((PPr3)-Pr-1)(2)] BF4(R = CH3(2),H(3)。F(4)) 。该“功能当量”也可以通过用1当量的HBF4对六氢化物OsH6(-)((PPr3)-Pr-1)(2)(5)进行质子化并随后释放三个氢分子来生成。一元氢化物也被5捕获。后者用0.5当量的HBF4质子化生成七氢化物二聚体[{OsH2((PPr3)-Pr-i)(2)}(2)(mu-H)(3)] BF4(6)。不会交换桥接和末端氢化物。

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