477884-90-5Relevant academic research and scientific papers
Chemistry on a metallathiaborane cluster Part 4: Reactions of 11-vertex rhodathiaboranes with bidentate phosphines and their subsequent rearrangements
Volkov, Oleg,Macias, Ramon,Rath, Nigam P,Barton, Lawrence
, p. 40 - 47 (2007/10/03)
The phosphine ligands on of the type [8,8-{η2-(CH2)n(PPh2)2}-8-{η1-(CH2) n(PPh2)2}-nido-8,7-RhSB9H10] (II), in the case of
Chemistry of a metallathiaborane cluster. 5. Reaction of [8,8-(η2-dppm)-8-(7eta;1-dppm)-nido-8,7-RhSB9 H10] and its derivatives with organotransition-metal reagents
Volkov, Oleg,Rath, Nigam P.,Barton, Lawrence
, p. 5505 - 5514 (2008/10/08)
The phosphine ligands on [8,8-(PPh3)2-mrfo-8,7-RhSB9H10] (2) may be replaced by the bidentate phosphine dppm {dppm = [(CH2)(PPh2)2]} to form the species [8,8-(η2-dppm)-8-(η1-dppm)-nido-8,7-RhSB9 H10] (3). The latter reacts with [Ru(η6-p-cym)(μ-Cl)2]2 to afford [8,8-η2-{(μ-Cl)2Ru(η6-p-cym)(dppm)}- nido-8,7-RhSB9H10] (4), which contains the group [(μ-Cl)2Ru-(η6-p-cym)(dppm)] that coordinates in a multidentate mode to Rh, in 77% yield. Similar chemistry using [Cp*Ir(μ-Cl)2]2 {Cp* = [η5-C5(CH3)5]} affords the related species [8,8-η2-{(μ-Cl)2Cp*Ir(dppm)}-nido-8,7-RhSB 9H10] (5), and [8,8-η2-{(μ-Cl)2Cp*Rh(dppm)}-nido-8,7-RhSB 9H10] (6) is obtained from the reaction between 2 and [Cp*RhCl2(η1-dppm)]. Reactions of 3 with [IrCl(CO)(PPh3)2] or [RhCl(PPh3)3] result in removal of dppm. [RhCl(PPh3)3] reacts with 3 to afford [1-PPh3-{l,3-(μ-dppm)}-closo-1,2-RhSB9H10] (7), but on reaction for extended periods [8-Cl-{8,9-(μ-dppm)}-10-PPh3-mdo-8,7-RhSB9H7 ] (8) is also formed. Reaction between 7 and dppe {dppe = [(CH2)2(PPh2)2]} gives [1,l-(η2-dppe)-3-(η1-dppm)-closo-l,2-RhSB9 H8] (9), which when treated with [Ru(η6-p-cym)(μ-Cl)2]2, affords [1.1-(η2-dppe)-3-η1-{(dppm)Ru(η6-p- cym)Cl2)}-closo-l,2-RhSB9H8] (10), in which the rhodathiaborane cage has a pendent metalligated dppm group at the 3-position. A rationale for the formation of 7 and 8 in the reaction of 3 with [RhCl(PPh3)3] is presented, and it provides evidence for the pathways for reactions of the other metal-containing moieties with 3. The existence of 8 provides support for some earlier proposals concerning the chemistry of 3. The new species 4, 5, 6, 8, and 10 are characterized by NMR spectroscopy, elemental analysis, mass spectrometry, and in the case of 4, 8, and 10, crystal structure determinations.
