Paul J. Ragogna

Bio: Paul J. Ragogna is an academic researcher from University of Western Ontario. The author has contributed to research in topics: Phosphonium & Ligand. The author has an hindex of 33, co-authored 115 publications receiving 2782 citations. Previous affiliations of Paul J. Ragogna include Dalhousie University & University of Alberta.

A germanium(II)-centered dication.

Abstract: The dicationic 42+ complex with three N-heterocyclic carbenes coordinated to a germanium center is reported. The complex was characterized by 1H NMR and FT Raman spectroscopy, and the structure was determined by single-crystal X-ray diffraction. Electronic structure calculations reveal a partial positive charge at germanium and that the germanium lone pair shows no evidence for π bonding.

Phosphine coordination complexes of the diphenylphosphenium cation: a versatile synthetic methodology for P-P bond formation.

Abstract: A series of phosphine−diphenylphosphenium donor−acceptor cationic complexes have been synthesized and comprehensively characterized (phosphine = diphenylchlorophosphine, triphenylphosphine, trimethylphosphine, and tricyclohexylphosphine). The complexes involve homoatomic P−P coordinate bonds that are susceptible to ligand exchange reactions highlighting a versatile new synthetic method for P−P bond formation. Phosphenium complexes of 1,2-bis(diphenylphosphino)benzene and 1,2-bis(tert-butylphosphino)benzene undergo unusual rearrangements to give a “segregated” diphosphine−phosphonium cation and a cyclic di(phosphino)phosphonium cation, respectively. The rearrangement products reveal the kinetic stability of the phosphine−phosphenium bonding arrangement.

Electronic structures of main-group carbene analogues.

Abstract: The electronic structures of 15 group 13-16 carbene analogues are analyzed using various quantum chemical methods and compared to the data obtained for the parent N-heterocyclic carbene (NHC), imidazol-2-ylidene. The results of this study present a uniform analysis of the similarities and differences in the electronic structures of p-block main-group carbene analogues. Though all systems are formally isovalent, the theoretical analyses unambiguously indicate that their electronic structures run the gamut from C=C localized (group 13) to C=N localized (group 16) via intermediate, more delocalized, systems. In particular, neither the stibenium ion nor any of the chalcogenium dications is a direct analogue of imidazol-2-ylidene as they all contain two lone pairs of electrons around the divalent main-group center, instead of the expected one. The reason behind the gradual change in the electronic structure of main-group analogues of imidazol-2-ylidene was traced to the total charge of the systems, which changes from anionic to dicationic when moving from left to right in the periodic table. Results from theoretical analyses of aromaticity show that all group 13-16 analogues of imidazol-2-ylidene display some degree of aromatic character. The heavier group 13 anions benefit the least from pi-electron delocalization, whereas the cationic group 15 systems are on par with the parent carbon system and display only slightly less aromatic character than cyclopentadienide, a true 6pi-electron aromatic species. The sigma-donor and pi-acceptor ability of the different main-group carbene analogues are also evaluated.

New synthetic opportunities using Lewis acidic phosphines

Abstract: Phosphines are traditional Lewis bases or ligands in transition metal complexes. In spite of their electron-rich (lone pair bearing) nature, an extensive coordination chemistry is developing for Lewis acidic phosphines, which highlights a new synthetic methodology leading to new structure and bonding.

Icephobic Behavior of UV-Cured Polymer Networks Incorporated into Slippery Lubricant-Infused Porous Surfaces: Improving SLIPS Durability

Abstract: Ice accretion causes damage on power generation infrastructure, leading to mechanical failure. Icephobic materials are being researched so that ice buildup on these surfaces will be shed before the weight of the ice causes catastrophic damage. Lubricated materials have imposed the lowest-recorded forces of ice adhesion, and therefore lubricated materials are considered the state-of-the-art in this area. Slippery lubricant-infused porous surfaces (SLIPS) are one type of such materials. SLIPS are initially very effective at repelling ice, but the trapped fluid layer that affords their icephobic properties is easily depleted by repeated icing/deicing cycles, even after one deicing event. UV-cured siloxane resins were infused into SLIPS to observe effects on icephobicity and durability. These UV-cured polymer networks enhanced both the icephobicity and longevity of the SLIPS; values of ice adhesion below 10 kPa were recorded, and appreciable icephobicity was maintained up to 10 icing/deicing cycles.

π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium

Abstract: This review is essentially an update of one entitled “πBonding and The Lone Pair Effect in Multiple Bonds Between Heavier Main Group Elements” which was published more than 10 years ago in this journal.1 The coverage of that survey was focused on the synthesis, structure, and bonding of stable compounds2 of heavier main group elements that correspond to the skeletal drawings reproduced in Tables 1 and 2. A row of numbers is listed at the bottom of each column in these tables. This refers to the number of stable complexes from each class that are currently known. The numbers in parentheses refer to the number of stable species that were known at the time of the previous review. Clearly, many of the compound classes listed have undergone considerable expansion although some remain stubbornly rare. The most significant developments for each class will be discussed in detail under the respective sections. As will be seen, there are also a limited number of multiple bonded heavier main group species that do not fit neatly in the classifications in Tables 1 and 2. However, to keep the review to a manageable length, the limits and exclusions, which parallel those used earlier, are summarized as follows: (i) discussion is mainly confined to compounds where experimental data on stable, isolated species have been obtained, (ii) stable compounds having multiple bonding between heavier main group elements and transition metals are not generally discussed, (iii) compounds in which a multiple bonded heavier main group element is incorporated within a ring are generally not covered, and (iv) hypervalent main group compounds that may incorporate faux multiple bonding are generally excluded. Such compounds are distinguished from those in Tables 1 and 2 in that they apparently require the use of more than four valence bonding orbitals at one or more of the bonded atoms. The remainder of this review is organized in a similar manner to that of the previous one wherein the compounds to be discussed are classified according to those summarized in Tables 1 and 2. The key unifying feature of almost all molecules discussed in this review is that they are generally stabilized by the use of bulky substituents which block associative or various decomposition pathways.3 Since the previous review was published in 1999, several review articles that cover parts of the subject matter have appeared.4

Quantifying and understanding the electronic properties of N-heterocyclic carbenes

Abstract: The use of N-heterocyclic carbenes (NHCs) in chemistry has developed rapidly over the past twenty years. These interesting compounds are predominantly employed in organometallic chemistry as ligands for various metal centres, and as organocatalysts able to mediate an exciting range of reactions. However, the sheer number of NHCs known in the literature can make the appropriate choice of NHC for a given application difficult. A number of metrics have been explored that allow the electronic properties of NHCs to be quantified and compared. In this review, we discuss these various metrics and what they can teach about the electronic properties of NHCs. Data for approximately three hundred NHCs are presented, obtained from a detailed survey of the literature.

Frustrated Lewis Pairs

Abstract: The articulation of the notion of “frustrated Lewis pairs” (FLPs), which emerged from the discovery that H2 can be reversibly activated by combinations of sterically encumbered Lewis acids and bases, has prompted a great deal of recent activity. Perhaps the most remarkable consequence has been the development of FLP catalysts for the hydrogenation of a range of organic substrates. In the past 9 years, the substrate scope has evolved from bulky polar species to include a wide range of unsaturated organic molecules. In addition, effective stereoselective metal-free hydrogenation catalysts have begun to emerge. The mechanism of this activation of H2 has been explored, and the nature and range of Lewis acid/base combinations capable of effecting such activation have also expanded to include a variety of non-metal species. The reactivity of FLPs with a variety of other small molecules, including olefins, alkynes, and a range of element oxides, has also been developed. Although much of this latter chemistry has...