Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]− (L2=chelating redox-active π-donor ligand)

In this article we present for the first time accurate density functional theory (DFT) and time-dependent (TD) DFT data for a series of electronically unsaturated five-coordinate complexes [Mn(CO)(3)(L-2)](-), where L-2 stands for a chelating strong pi-donor ligand represented by catecholate, dithiolate, amidothiolate, reduced alpha-diimine (1,4-dialkyl-1,4-diazabutadiene (R-DAB), 2,2'-bipyridine) and reduced 2,2'-biphosphinine types. The single-crystal X-ray structure of the unusual compound [Na(BPY)][Mn(CO)(3)(BPY)]center dot Et2O and the electronic absorption spectrum of the anion [Mn(CO)(3)(BPY)](-) are new in the literature. The nature of the bidentate ligand determines the bonding in the complexes, which varies between two limiting forms: from completely pi-delocalized diamagnetic {(CO)(3)Mn-L-2}(-) for L-2 = alpha-diimine or biphosphinine, to largely valence-trapped {(CO)(3)Mn-1-L-2(2-)}(-) for L-2(2-) = catecholate, where the formal oxidation states of Mn and L-2 can be assigned. The variable degree of the pi-delocalization in the Mn(L-2) chelate ring is indicated by experimental resonance Raman spectra of [Mn(CO)(3)(L-2)](-) (L-2=3,5-di-tBu-catecholate and iPr-DAB), where accurate assignments of the diagnostically important Raman bands have been aided by vibrational analysis. The L-2 = catecholate type of complexes is known to react with Lewis bases (CO substitution, formation of six-coordinate adducts) while the strongly pi-delocalized complexes are inert. The five-coordinate complexes adopt usually a distorted square pyramidal geometry in the solid state, even though transitions to a trigonal bipyramid are also not rare. The experimental structural data and the corresponding DFT-computed values of bond lengths and angles are in a very good agreement. TD-DFT calculations of electronic absorption spectra of the studied Mn complexes and the strongly pi-delocalized reference compound [Fe(CO)(3)(Me-DAB)] have reproduced qualitatively well the experimental spectra. Analyses of the computed electronic transitions in the visible spectroscopic region show that the lowest-energy absorption band always contains a dominant (in some cases almost exclusive) contribution from a pi(HOMO) -> pi*(LUMO) transition within the MnL2 metallacycle. The character of this optical excitation depends strongly on the composition of the frontier orbitals, varying from a partial L-2 -> Mn charge transfer (LMCT) through a fully delocalized pi(MnL2) -> pi*(MnL2) situation to a mixed (CO)Mn -> L-2 charge transfer (LLCT/MLCT). The latter character is most apparent in the case of the reference complex [Fe(CO)(3)(Me-DAB)]. The higher-lying, usually strongly mixed electronic transitions in the visible absorption region originate in the three lower-lying occupied orbitals, HOMO - 1 to HOMO - 3, with significant metal-d contributions. Assignment of these optical excitations to electronic transitions of a specific type is difficult. A partial LLCT/MLCT character is encountered most frequently. The electronic absorption spectra become more complex when the chelating ligand L-2, such as 2,2'-bipyridine, features two or more closely spaced low-lying empty pi* orbitals.

Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp′]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp′=Cp; L2=dppe; Cp′=Cp∗)

A series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(C CAr)(L-2)Cp'] (Ar = phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2 = (PPh3)(2), Cp' = Cp; L-2 = dppe; Cp' = Cp*) have been examined using electrochemical and spectroelectrochemical methods. One-electron oxidation of these complexes gave the corresponding radical cations [Ru(C CAr)(L2)Cp'](+). Those cations based on Ru(dppe)Cp*, or which feature a para-tolyl acetylide substituent, are more chemically robust than examples featuring the Ru(PPh3)(2)Cp moiety, permitting good quality UV-Vis-NIR and IR spectroscopic data to be obtained using spectroelectrochemical methods. On the basis of TD DFT calculations, the low energy (NIR) absorption bands in the experimental electronic spectra for most of these radical cations are assigned to transitions between the beta-HOSO and beta-LUSO, both of which have appreciable metal d and ethynyl pi character. However, the large contribution from the anthryl moiety to the frontier orbitals of [Ru(C CC14H9)(L2)CP'](+) suggests compounds containing this moiety should be described as metal-stabilised anthryl radical cations.

Comprehension of reflexives and pronouns in sequential bilingual children: do they pattern similarly to L1 children, L2 adults, or children with specific language impairment?

This paper investigates how sequential bilingual (L2) Turkish-English children comprehend English reflexives and pronouns and tests whether they pattern similarly to monolingual (L1) children, L2 adults, or children with Specific Language Impairment (SLI). Thirty nine 6- to 9-year-old L2 children with an age of onset of 30-48 months and exposure to English of 30-72 months and 33 L1 age-matched control children completed the Advanced Syntactic Test of Pronominal Reference-Revised (van der Lely, 1997). The L2 children’s performance was compared to L2 adults from Demirci (2001) and children with SLI from van der Lely & Stollwerck (1997). The L2 children’s performance in the comprehension of reflexives was almost identical to their age-matched controls, and differed from L2 adults and children with SLI. In the comprehension of pronouns, L2 children showed an asymmetry between referential and quantificational NPs, a pattern attested in younger L1 children and children with SLI. Our study provides evidence that the development of comprehension of reflexives and pronouns in these children resembles monolingual L1 acquisition and not adult L2 acquisition or acquisition of children with SLI.

Language dominance and lexical diversity: how bilinguals and L2 learners differ in their knowledge and use of French lexical and functional items

This chapter compares lexical diversity of French words used by Dutch-French bilinguals, English-French bilinguals and Flemish L2 learners of French.

Selective listening in L2 learners of French

This paper considers the issue raised by Brown (2008) regarding whether nouns are ‘privileged’ in memory over verbs during listening tasks, and whether attention to nouns, at least in the early stages of L2 learning, is a desirable strategy to be taught to learners, as Brown suggests it might be. The question of verb/noun recognition was explored in the present study using data from 30 lower-intermediate learners of French in England. Learners completed a listening task on two occasions, six months apart, producing recall protocols for short oral passages in French. We also explored learners’ attentional strategy use by asking them to report on this in writing immediately after the recall task. An analysis of verbs and nouns recognised indicated that verb recognition was lower than that of nouns, and that progress in verb recognition over six months was negligible. A qualitative analysis of learners’ strategy use indicated that learners with a more balanced verb/noun recognition profile took a broader focus, tending to focus their attention consciously at phrase/sentence level rather than at word level. These findings are discussed in terms of the development of listening skills over time, and the implications of this for L2 listening pedagogy.

New perspectives on transfer among bilinguals and L2 users

This is a special issue of the International Journal of Bilingualism. This special issue brings together approaches to transfer in L2 learners, bilinguals, multilinguals and attriters. Researchers working in SLA are often unaware of research done on transfer in bilinguals and vice versa, and this special issue bridges important gaps between researchers from a range of fields.