title: Intramolecular alkyl phosphine dehydrogenation in cationic rhodium complexes of tris(cyclopentylphosphine).
abstract: [Rh(nbd)(PCyp(3))(2)][BAr(F) (4)] (1) [nbd = norbornadiene, Ar(F) = C(6)H(3)(CF(3))(2), PCyp(3) = tris(cyclopentylphosphine)] spontaneously undergoes dehydrogenation of each PCyp(3) ligand in CH(2)Cl(2) solution to form an equilibrium mixture of cis-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(2)][BAr(F) (4)] (2 a) and trans-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(2)][BAr(F) (4)] (2 b), which have hybrid phosphine-alkene ligands. In this reaction nbd acts as a sequential acceptor of hydrogen to eventually give norbornane. Complex 2 b is distorted in the solid-state away from square planar. DFT calculations have been used to rationalise this distortion. Addition of H(2) to 2 a/b hydrogenates the phosphine-alkene ligand and forms the bisdihydrogen/dihydride complex [Rh(PCyp(3))(2)(H)(2)(eta(2)-H(2))(2)][BAr(F) (4)] (5) which has been identified spectroscopically. Addition of the hydrogen acceptor tert-butylethene (tbe) to 5 eventually regenerates 2 a/b, passing through an intermediate which has undergone dehydrogenation of only one PCyp(3) ligand, which can be trapped by addition of MeCN to form trans-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(PCyp(3))(NCMe)][BAr(F) (4)] (6). Dehydrogenation of a PCyp(3) ligand also occurs on addition of Na[BAr(F) (4)] to [RhCl(nbd)(PCyp(3))] in presence of arene (benzene, fluorobenzene) to give [Rh(eta(6)-C(6)H(5)X){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (7: X = F, 8: X = H). The related complex [Rh(nbd){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] 9 is also reported. Rapid ( approximately 5 minutes) acceptorless dehydrogenation occurs on treatment of [RhCl(dppe)(PCyp(3))] with Na[BAr(F) (4)] to give [Rh(dppe){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (10), which reacts with H(2) to afford the dihydride/dihydrogen complex [Rh(dppe)(PCyp(3))(H)(2)(eta(2)-H(2))][BAr(F) (4)] (11). Competition experiments using the new mixed alkyl phosphine ligand PCy(2)(Cyp) show that [RhCl(nbd){PCy(2)(Cyp)}] undergoes dehydrogenation exclusively at the cyclopentyl group to give [Rh(eta(6)-C(6)H(5)X){PCy(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (17: X = F, 18: X = H). The underlying reasons behind this preference have been probed using DFT calculations. All the complexes have been characterised by multinuclear NMR spectroscopy, and for 2 a/b, 4, 6, 7, 8, 9 and 17 also by single crystal X-ray diffraction.
authors.affiliation: Department of Chemistry, University of Bath, Bath BA2 7AY, UK.
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Douglas
authors.forename: Simon K
authors.initials: SK
authors.lastname: Brayshaw
authors.forename: Romaeo
authors.initials: R
authors.lastname: Dallanegra
authors.forename: Gabriele
authors.initials: G
authors.lastname: Kociok-Köhn
authors.forename: Stuart A
authors.initials: SA
authors.lastname: Macgregor
authors.forename: Gemma L
authors.initials: GL
authors.lastname: Moxham
authors.forename: Andrew S
authors.initials: AS
authors.lastname: Weller
authors.forename: Tebikie
authors.initials: T
authors.lastname: Wondimagegn
authors.forename: Prabha
authors.initials: P
authors.lastname: Vadivelu
mesh_terms: D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D003517:Cyclopentanes; D006859:Hydrogen / Q000737:chemistry; D006865:Hydrogenation; D008024:Ligands; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D013997:Time Factors
chemical_list: D002412:Cations; D003517:Cyclopentanes; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; C527936:tris(cyclopentylphosphine); D006859:Hydrogen; D012238:Rhodium