Fluxional rhodium scorpionate complexes of the hydrotris(methimazolyl)borate (Tm) ligand and their static boratrane derivatives.

LÓPEZ-GÓMEZ, María J, CONNELLY, Neil G, HADDOW, Mairi F, HAMILTON, Alexander and ORPEN, A Guy (2010). Fluxional rhodium scorpionate complexes of the hydrotris(methimazolyl)borate (Tm) ligand and their static boratrane derivatives. Dalton Transactions, 39 (22), 5221-5230.

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Link to published version:: 10.1039/C000651C

Abstract

The reaction of potassium hydrotris(methimazolyl)borate {KTm = HB(mt)(3)} with [{Rh(cod)(mu-Cl)}(2)] gave [Rh(cod)Tm] while the complexes [Rh(CO)(PR(3))Tm] (R = Ph or NMe(2)) and [Rh{P(OPh)(3)}(2)Tm] were isolated from light-sensitive [Rh(CO)(2)Tm], prepared in situ from KTm and [{Rh(CO)(2)(mu-Cl)}(2)], and PR(3) or P(OPh)(3) under CO. The complexes [Rh(cod)Tm] and [Rh(CO)(PR(3))Tm] (R = Ph or NMe(2)) adopt kappa(3)-S(2)H structures in the solid state but in all cases rapid dynamic exchange processes render the three mt rings equivalent in solution. Oxidation of [Rh(CO)(PPh(3))Tm] with [Fe(eta-C(5)H(5))(2)][PF(6)] in the presence of NHPr(i)(2) gave a mixture containing two monocationic rhodaboratranes. One is assigned as [Rh(CO)(PPh(3)){B(mt)(3)}][PF(6)] on the basis of IR and NMR spectroscopy, with boron trans to the phosphine ligand. The second, structurally characterised as [Rh(PPh(3)){B(mt)(3)}][PF(6)], has boron trans to an empty coordination site, vacated by CO. Similar oxidation of [Rh(cod)Tm] gave small quantities of the boron-fluorinated bis(scorpionate) [Rh{FB(mt)(3)}(2)][PF(6)].

Item Type: Article
Research Institute, Centre or Group: Biomolecular Sciences Research Centre
Identification Number: 10.1039/C000651C
Depositing User: Jamie Young
Date Deposited: 29 May 2015 11:02
Last Modified: 29 May 2015 11:02
URI: http://shura.shu.ac.uk/id/eprint/9933

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