Triarylamminium radical-cation complexes: design and magnetic properties and Base-catalyzed hydrosilylation: mechanism and substrate scope

1. Triarylamminium radical-cation complexes. The detailed study of manganese, copper and nickel metal-radical complexes with triarylamminium ligands was conducted. Stable, neutral and pseudo-octahedral coordination monometallic complexes with simple monodentate 2,2`-bipyridine ligand containing a redox-active N,N`-(4,4`-dimethoxydiphenyl-amino) substituent were synthesized and fully characterized. The one-electron oxidation process and formation of persistent radical-cation complexes was observed by cyclic voltammetry and spectroelectrochemical measurements. Evans method measurements were performed with radical-cation complexes generated by chemical one-electron oxidation with NOPF6 in acetonitrile. The experimental results indicate ferromagnetic coupling between metal and triarylamminium cation in manganese (II) complex and antiferromagnetic coupling in nickel (II) complex. This data is supported by DFT calculations which also lend weight to the  spin polarization mechanism as an operative model for magnetic exchange coupling. Neutral bimetallic complexes with a new ditopic ligand were synthesized and fully characterized, including magnetic and electrochemical studies. Chemical oxidation of these precursor complexes did not generate radical-cations, but dicationic complexes, which was confirmed by UV-vis and EPR-experiments, as well as varied temperature magnetic measurements. DFT calculations for radical-cation complexes are included. A synthetic pathway for polytopic ligand with multiple redox-active triarylamine sites was developed. The structure of the ligand is presumably suitable for -spin polarization exchange model and allows for production of polymetallic complexes having high spin ground states. 2. Base-catalyzed hydrosilylation. A simple reductive base-catalyzed hydrosilation of aldehydes and ketones was adapted to the use of the cheap, safe, and non-toxic polymethylhydrosiloxane (PMHS) instead of the common PhSiH3 and (EtO)3SiH, which present significant cost and safety concerns, respectively. The conversion of silane into pentacoordinate silicate species upon addition of a base was studied in details for the cases of phenyl silane and PMHS and is believed to be essential for the hydrosilylation process. We discovered that nucleophiles (a base or fluoride-anion) induced the rearrangement of PMHS and TMDS into light silanes: MeSiH3 and Me2SiH2, respectively. The reductive properties of PMHS under basic conditions can be attributed to the formation of methyl silane and its conversion into a silicate species. A procedure for the generation of methyl silane and its use in further efficient reductions of aldehydes and ketones has been developed. The protocol was extended to the selective reduction of esters and tertiary amides into alcohols and aldimines into amines with good isolated yields and reduction of heterocyclic compounds was attempted.

Alberta Price List No. 3., January 1st, 1925

A price list form for the Alberta Liquor Control Board from 1 January 1925. The price list includes "General Information" in regards to permits for individuals and special permits. The alcohol is then listed by category for pricing: Scotch Whisky, Irish Whisky, Rye Whisky, Bourbon Whisky, Rum, Gin, Brandy, Port, Native Wine, Italian (Type) Wines, Sherry, Claret, Burgundy, White Wine, Sparkling Wine, Vermouth, Cocktails, Liqueurs, Champagne, Bitters, Ale and Stout, Chinese Liquors.

General Price List, Ontario, 1 January 1924

A general price list from the year 1924 for the province of Ontario. The cover of the list reads: "Ontario Government Dispensaries Conducted Under Direction of Board of License Commissioners for Ontario By Authority of The Ontario Temperance Act. General Price List, Dispensaries sell liquor for medicinal, sacramental, scientific and manufacturing purposes only. The sale of liquor for beverage purposes in the Province of Ontario is prohibited by The Ontario Temperance Act. Dispensaries: No.1-154 Wellington Street West, Toronto; No.2-1271 Dundas Street West, Toronto; No.3-29 Charles Street, Hamilton; No.4-425 Talbot Street, London; No.5-30 Sandwich Street West, Windsor; No.6-Golden Lion Block, Kingston; No.7-92 Kent Street, Ottawa; No.8-109 Simpson Street, Fort William."

Newfoundland Price List, 1 June 1928

A price list for Newfoundland by the Board of Liquor Control, St. John's. The list is one page in length and has a few handwritten changes to prices.

Price List - Lawrence A. Wilson Co. Limited, 1916

A price list for Lawrence A. Wilson Co. Limited, 87 James St., Montreal Quebec. It is addressed to The Toronto Hunt, 52 Bay Street, Toronto. There are additional handwritten notes. One of the handwritten notes reads "ck to W. Stephen Haas"

Wiehl & Widmann Price List, August 1903

A price list for Wiehl & Widmann (Wholesale Importers of and Dealers in Wines, Liquors and Mineral Waters). The price list is dated August 1903 and the location of the dealer is New York.

The "Bodega" Company Price List

A price list for The "Bodega" Company Limited. The company has branches throughout the United Kingdom, including: London, Birmingham, Manchester, Liverpool, Glasgow, Edinburgh, Dundee, Brighton, and Ryde. The final pages of the price list also include a reprinted article from "The Irish Times" concerning a case against the use of the Bodega Company name.

Artists Rendering of Isobel Price

Artist’s rendering in colour of Isobel Price in an oval frame with a hook at the top and a section at the back which contains a lock of hair. This painting was done by Gerald Sinclair Hayward who was a renowned artist whose work was displayed at an exhibition in New York in 1899. He painted Theodore Roosevelt, William K. Vanderbilt and members of the ruling families of Britain, Germany and Russia. The frame is enclosed in a folding case lined with velvet and silk. The silk is quite worn. The outside of the case appears to be leather and has a stand for setting it upright. It closes with a metal latch. This is accompanied by a note by R. Band.

Indenture between Samuel Street and Eunice Price

Indenture (vellum) of bargain and sale between Samuel Street of Stamford and Eunice Price widow of the late David Price of Willoughby regarding a part of Lot no. 15 in the 5th Concession in Humberstone - instrument no. 1141, June 14, 1842.

Letter to Isabel from Phil [Phil Ingram Price]

Letter to Isabel from Phil [Phil Ingram Price] in which he expresses a desire to divide the estate with as little delay as possible. He has divided the books into 4 lots, but he asks if Isabel has some of the books as they are missing, March 28, 1900.

Letter to Isabel from someone whose last name is Price [the first name is illegible]

Letter to Isabel from someone whose last name is Price [the first name is illegible] in which the writer says that the row with Phil regarding the bonds is settled (1 ½ pages). This person does not anticipate any more trouble with Phil. They are sending the personal effects to Isabel as well as a cheque for $3000 as her share of the estate, and more next month, July 15, 1901.

Estimate of road price from Port Robinson to Beaverdams Road

Estimate of road price from Port Robinson to Beaverdams Road, n.d.

Mirroring Enzymes: The Role of H-Bonding In HQuin-BAM Catalyzed Asymmetric Aza-Henry Reactions: A DFT Study into the Reactivity, Mechanism, and Origins of Selectivity

The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.

Letter to P.I. Price asking him to make out a cheque in favour of German and Pettit for looking after certain petitions in Willoughby and Bertie Townships and in Welland

Letter to P.I. Price asking him to make out a cheque in favour of German and Pettit for looking after certain petitions in Willoughby and Bertie Townships and in Welland. This is signed by H.H. Collier, March 5, 1906.

Letter to Mr. Price from E.J. McIntryre regarding a cheque for the assessment on a railway

Letter to Mr. Price from E.J. McIntryre regarding a cheque for the assessment on a railway, Dec. 25, 1910.