Heterolytic H2 activation on a carbene-ligated rhodathiaborane promoted by isonido-nido cage opening.
نویسندگان
چکیده
A new mechanism of H2 activation is reported to occur on a carbene-ligated rhodathiaborane that features metal-thiaborane bifunctional synergistic effects. The key is the creation of vacant coordination sites by an isonido-nido structural transformation leading to the heterolytic H-H bond splitting.
منابع مشابه
Unusual cationic rhodathiaboranes: synthesis and characterization of [8,8,8-(H)(PR3)2-9-(Py)-nido-8,7-RhSB9H10]⁺ and [1,3-μ-(H)-1,1-(PR3)2-3-(Py)-isonido-1,2-RhSB9H8]⁺.
The treatment of the hydridorhodathiaboranes, [8,8,8-(H)(PR3)2-9-(Py)-nido-8,7-RhSB9H9], where PR3 = PPh3 (2), PMePh2 (3), PPh3 and PMe2Ph (4), or PMe3 and PPh3 (5), and [8,8,8-(H)(PMePh2)2-9-(PMePh2)-nido-8,7-RhSB9H9] (6), with TfOH affords [8,8,8-(H)(PR3)2-9-(Py)-nido-8,7-RhSB9H10](+) cations, where PR3 = PPh3 (12), PMePh2 (13), PPh3 and PMe2Ph (14), or PMe3 and PPh3 (15), and [8,8,8-(H)(PMeP...
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The reaction of [8,8-(PPh(3))(2)-nido-8,7-RhSB(9)H(10)] (1) with PR(3) in a 1:2 ratio affords mixtures that contain the mono-substituted bis-PR(3)-ligated rhodathiaboranes [8,8-(PPh(3))(L)-nido-8,7-RhSB(9)H(10)] [L = PMe(2)Ph (5), PMe(3) (6)] and the corresponding tris-PR(3)-ligated compounds [8,8,8-(L)(3)-nido-8,7-RhSB(9)H(10)] [L = PMe(2)Ph (7), PMe(3) (8)]. These latter species are more conv...
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The treatment of [1,1-(PR3 )2 -3-(Py)-closo-1,2-RhSB9 H8 ] (PR3 =PMe3 (2) or PPh3 and PMe3 (3); Py=pyridine) with triflic acid (TfOH) affords [1,3-μ-(H)-1,1-(PR3 )2 -3-(Py)-1,2-RhSB9 H8 ](+) (PR3 =PMe3 (4) or PMe3 and PPh3 (5)). These products result from the protonation of the 11-vertex closo-cages along the Rh(1)B(3) edge. These unusual cationic rhodathiaboranes are stable in solution and in...
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عنوان ژورنال:
- Chemical communications
دوره 49 84 شماره
صفحات -
تاریخ انتشار 2013