Alkynylcyclohexadienyl tricarbonyliron complexes: A new directing effect for organoiron-mediated synthesis

The first example of an alkyne-substituted tricarbonyl(η⁵-cyclohexadienyl)iron(1+) complex has been prepared and the ω directing effect of the phenylethynyl substituent has been demonstrated in nucleophile addition reactions. Addition of NC⁻ also occurs at the a position to form an unusual η¹, η³-structure.     

Experimental probes of silver metal nanoparticle formation kinetics: Comparing indirect versus more direct methods

The kinetics of noble metal nanoparticle formation in bottom-up syntheses are important for controlling and optimizing these methods. Hence, experimental probes that are easily accessible to most laboratories are also of interest. We collected kinetic curves for the formation of silver nanoparticles in a modified Turkevich method with citrate acting as the reducing and stabilizing agent by (i) measuring the change in silver nanoparticle surface plasmon resonance by UV-visible spectroscopy, a somewhat indirect method, and then also by (ii) measuring the change in silver ion concentration by ion-selective electrode potentiometry and/or atomic absorption spectroscopy, two more direct methods. The resulting sigmoidal kinetic curves were curvefitted with the Finke-Watzky two-step kinetic model of slow, continuous nucleation and fast autocatalytic growth to extract average rate constants. We found that the kinetic curves obtained by following the change in silver ion concentration were apparent mirror images of those constructed by following the change in nanoparticle surface plasmon resonance, and that their respective curvefits displayed the same sigmoidal characteristics. The resultant values of the rate constants for nucleation and growth overlapped within experimental error between the methods and showed similar trends over the range of citrate concentrations studied. The use of multiple probes in this work to follow the kinetics of nanoparticle formation helps fill a need for the comparison and evaluation of different methods available to scientists, particularly those considered easily accessible.     

Selective synthesis and reactivity of eta5-arylcyclohexadienyliron complexes

A series of aryl-substituted cyclohexadienyliron complexes have been prepared by a general procedure that determines regioselectivity by correctly positioning leaving groups in the precursor complexes. The aryl groups at 1-C or 2-C have been shown to be omega directing by the study of reactions with a representative range of nucleophiles, and these regioselectivity properties have been related to the spectroscopic properties of the cationic cyclohexadienyliron complexes. A high level of electron-donating substituents on the arene, or switching between the [Fe(CO)3] and [Fe(CO)2PPh3] series, reduces the minor ipso pathway, improving regiocontrol. Placing opposed directing groups in the arylcyclohexadienyliron complexes reverts reactivity to the ipso pathway with stabilised enolate nucleophiles, and when the additional directing group reinforces the effect of the aryl group, the ipso pathway is stopped.     

On <Emphasis Type="Italic">g</Emphasis>-functions for Laguerre function expansions of Hermite type

We examine weighted L ^p boundedness of g-functions based on semigroups related to multi-dimensional Laguerre function expansions of Hermite type. A technique of vector-valued Calderón–Zygmund operators is used.