Static solid-state (35)Cl (I = (3)/(2)) NMR spectra of the organometallic compounds Cp(2)TiCl(2), CpTiCl(3), Cp(2)ZrCl(2), Cp(2)HfCl(2), Cp*(2)ZrCl(2), CpZrCl(3), Cp*ZrCl(3), Cp(2)ZrMeCl, (Cp(2)ZrCl)(2)mu-O, and Cp(2)ZrHCl (Schwartz's reagent) have been acquired at 9.4 T with the quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) sequence in a piecewise manner. Spectra of several samples have also been acquired at 21.1 T. The electric field gradient (EFG) tensor parameters, the quadrupolar coupling constant (C(Q)) and quadrupolar asymmetry parameter (eta(Q)), are readily extracted from analytical simulations of the spectra. The (35)Cl EFG and chemical-shift tensor parameters are demonstrated to be sensitive probes of metallocene structure and allow for differentiation of monomeric and oligomeric structures. First-principles calculations of the (35)Cl EFG parameters successfully reproduce the experimental values and trends. The origin of the observed values of C(Q)((35)Cl) are further examined with natural localized molecular orbital (NLMO) analyses. The combination of experimental and theoretical methods applied to the model compounds are employed to structurally characterize Schwartz's reagent (Cp(2)ZrHCl), for which a crystal structure is unavailable. Aside from a few select examples of single-crystal NMR spectra, this is the first reported application of solid-state (35)Cl NMR spectroscopy to molecules with covalently bound chlorine atoms. It is anticipated that the methodology outlined herein will find application in the structural characterization of a wide variety of chlorine-containing transition-metal and main-group systems.

An in situ redox method is employed to prepare N-heterocyclic bromophosphines in good yield and purity. Such bromophosphines may be treated with a variety of bromide-abstracting reagents to produce the corresponding N-heterocyclic phosphenium salts in excellent yield.Salts containing phosphenium cations have played an important role in the history and development of modern maingroup chemistry. In the most general definition, a phosphenium cation ( 1) is a cation that contains a dicoordinate phosphorus center bearing a total of six valence electrons and is the isovalent analogue of a carbene (2). 1,2 While numerous types of phosphenium cations have been prepared and studied, the most important class of phosphenium compounds is the relatively stable species in which the dicoordinate phosphorus center is supported by two adjacent amido substituents. Although such compounds are analogous to the now-ubiquitous N-heterocyclic carbenes (NHCs, 3) 3,4 and may be labeled N-heterocyclic phosphenium cations (NHPs, 4), it is worth noting that well-characterized NHPs were reported more than 35 years ago 5,6 and thus predate the first report of a stable NHC considerably. In fact, the structural characterization of a salt containing a 1,3,2-diazaphospholenium cation, an unsaturated NHP directly analogous to the most common type of "Arduengo" NHC, 7 was reported as early as 1990. 8

Analytically pure chloride and bromide salts of two different cyclic triphosphenium cations are prepared by the reaction of PX3 (X=Cl, Br) in the presence of the halogen-scavenging reagent cyclohexene. For the brominated species, the neutral, volatile 1,2-dibromocyclohexane byproduct is readily removed under reduced pressure, and the desired salts are obtained in high yield. Reactions involving phosphorus trichloride are complicated by the formation of salts containing both chloride and hydrogen dichloride anions. Reactivity experiments on potential undesired halogenated diphosphine byproducts suggest that the formation of such species can be prevented by increasing the concentration of cyclohexene employed in the reaction.

Tannins are a group of polyphenols found in fruits, leaves, trees, etc., well known in the leather industry and in apples, persimmons and grapes, because of their capacity to interact with other polyphenols or other components either from the food product or from saliva. Prior to being able to interact with other compounds, tannins have to be extracted from the food matrix, which depends on their chemistry, as well as the chemical structure of other components, such as cell wall material and proteins. Vitis vinifera grapes are commonly grown around the world and are used in winemaking, providing good quality wines with different levels of tannins responsible for the final wine’s astringency. Many studies have focused on tannins extractability and retention with cell wall material, and the reactivity of tannins with proteins in Vitis vinifera grapes and wine, but there are very few reports for other Vitis species. However, depending on the environmental characteristics of certain regions, Vitis hybrid grapes are grown and used to produce wines more and more. This review focuses on the comparison of the chemistry of tannins, and their reactivity with other macromolecules in Vitis species.