Reactions of monosubstituted alkanes with bare metal ions.

Reactions of C5H5M+ (M=Fe, Ni) with substituted thiophenes

“…As a consequence in the reactions with loss of HX the [3] formation of a new C-C bond between the thiophene ring and the cyclopentadienylic ring is highly probable.…”

“…1, the variation of the relative intensity for the reactant and product ions is shown for the reaction of NiC 5 H þ 5 with 2-chloro thiophene as function of the reaction time up to 500 ms; the behaviour is typical of a consecutive reaction; in addition after the isolation of the ion [2] it can react again with 2-chloro thiophene to form the end product [3]; this is the only reaction observed for the ions [2] which do not show any decomposition reaction when subject to a tickle frequency to increase the energy of collisions with the buffer gas.…”

“…Product [1] is the addition ion; [2] is a product which results from the loss of HR from the addition; [3] is formed by the addition of a second thiophene molecule and loss of another HR molecule. The addition ion [1] is observed with the unsubstituted thiophene and in the reaction of 2-methyl thiophene with C 5 H 5 Fe + and C 5 H 5 Ni + , this ion does not give rise to further reaction; in the reactions of the halogen substituted thiophenes we do not observe any addition product but only products [2] and [3] are present, loss of HR was found also in the reaction of the ion C 5 H 5 Ni + with 2-methyl thiophene.…”

“…After the explosion [2,3] of investigations in the ion-molecule reactions between free metal ions and organic molecules chiefly aimed to explore the possibility of C-C and C-H bonds activation, studies of coordinated metals ions indicated several interesting reactivity differences [2]. In spite of the fact that the Cp(g 5 -C 5 H 5 ) ligand is very common in the organometallic chemistry and its complexes are widely employed in several reaction of industrial relevance [4] the reaction of cyclopentadienylic transition metals complexes are not studied very extensively.…”

Inherent Asymmetry of Constitutionally Equivalent Methyl Groups in the H/D Equilibration ofn- andi-C3H7Fe(OH)+ Complexes

“…In general, water loss is believed to commence with complexation of the metal cation at oxygen, followed by oxidative insertion into the CÀO bond (Scheme 2: 1 32 or 1' 32'). [1,2] Next, b-hydrogen transfers lead to either a hydrido hydroxy complex 3 or directly [3] to the bisligated complex 4; the latter decomposes preferentially by loss of water, because H 2 O is less strongly bound to Fe than propene. [4] In fact, the metastable ions 1 and 1' show almost exclusive elimination of water (b 99 %) on the microsecond time scale.…”