title: Can a pentamethylcyclopentadienyl ligand act as a proton-relay in f-element chemistry? Insights from a joint experimental/theoretical study.
abstract: Isomerisation of buta-1,2-diene to but-2-yne by (Me(5)C(5))(2)Yb is a thermodynamically favourable reaction, with the Δ(r)G° estimated from experimental data at 298 K to be -3.0 kcal mol(-1). It proceeds in hydrocarbon solvents with a pseudo first-order rate constant of 6.4 × 10(-6) s(-1) and 7.4 × 10(-5) s(-1) in C(6)D(12) and C(6)D(6), respectively, at 20 °C. This 1,3-hydrogen shift is formally forbidden by symmetry and has to occur by an alternative pathway. The proposed mechanism for buta-1,2-diene to but-2-yne isomerisation by (Me(5)C(5))(2)Yb involves coordination of methylallene (buta-1,2-diene) to (Me(5)C(5))(2)Yb, and deprotonation of methylallene by one of the Me(5)C(5) ligands followed by protonation of the terminal methylallenyl carbon to yield the known coordination compound (Me(5)C(5))(2)Yb(η(2)-MeC[triple bond, length as m-dash]CMe). Computationally, this mechanism is not initiated by a single electron transfer step, and the ytterbium retains its oxidation state (II) throughout the reactivity. Experimentally, the influence of the metal centre is discussed by comparison with the reaction of (Me(5)C(5))(2)Ca towards buta-1,2-diene, and (Me(5)C(5))(2)Yb with ethylene. The mechanism by which the Me(5)C(5) acts as a proton-relay within the coordination sphere of a metal also rationalises the reactivity of (i) (Me(5)C(5))(2)Eu(OEt(2)) with phenylacetylene, (ii) (Me(5)C(5))(2)Yb(OEt(2)) with phenylphosphine and (iii) (Me(5)C(5))(2)U(NPh)(2) with H(2) to yield (Me(5)C(5))(2)U(HNPh)(2). In the latter case, the computed mechanism is the heterolytic activation of H(2) by (Me(5)C(5))(2)U(NPh)(2) to yield (Me(5)C(5))(2)U(H)(HNPh)(NPh), followed by a hydrogen transfer from uranium back to the imido nitrogen atom using one Me(5)C(5) ligand as a proton-relay. The overall mechanism by which hydrogen shifts using a pentamethylcyclopentadienyl ligand as a proton-relay is named Carambole in reference to carom billiards.
authors.affiliation: LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, Toulouse 31077, France. laurent.maron@irsamc.ups-tlse.fr.
authors.forename: Christos E
authors.initials: CE
authors.lastname: Kefalidis
authors.forename: Lionel
authors.initials: L
authors.lastname: Perrin
authors.forename: Carol J
authors.initials: CJ
authors.lastname: Burns
authors.forename: David J
authors.initials: DJ
authors.lastname: Berg
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron
authors.forename: Richard A
authors.initials: RA
authors.lastname: Andersen
mesh_terms: D003517:Cyclopentanes / Q000737:chemistry*; D008024:Ligands; D009942:Organometallic Compounds / Q000737:chemistry*; D011522:Protons; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D003517:Cyclopentanes; D008024:Ligands; D009942:Organometallic Compounds; D011522:Protons