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.

Indenture between Robert Miller of the County of La Porte, Indiana and Asat Carpenter of the Town of Niagara regarding 50 acres in the Township of Southwold, Middlesex

Indenture between Robert Miller of the County of La Porte, Indiana and Asat Carpenter of the Town of Niagara regarding 50 acres in the Township of Southwold, Middlesex. There are 2 copies of this document tin which the wording seems slightly different. The 1st copy is slightly burned on the side and extremely faded, making it completely illegible. The 2nd copy is legible. Feb. 15, 1853

Article of agreement between Alexander Cook, contractor of Humberstone and the Provisional Municipal Council of the county of Welland

Article of agreement between Alexander Cook, contractor of Humberstone and the Provisional Municipal Council of the county of Welland to construct and build the main drain through the marsh lands tract commencing in lot no. 27 in the 4th concession in the township of Humberstone in a southerly direction (6 pages, handwritten). This is signed by John Frazer, Provisional Warden, Dexter Deverardo and Alexander Cook. (2 copies), Dec. 30, 1854.

Memo to the warden and councilors for the County of Welland in council assembled regarding the contract of Edward Henderson

Memo to the warden and councilors for the County of Welland in council assembled regarding the contract of Edward Henderson. The terms of the contract have not been exceeded. This note is not signed, n.d.

Synthesis of 4-hydroxycinnamic amides of di-, tri-, and tetraamines : potential insect toxins /

The monoconjugates of phenolic acids (i.e. coumaric acid) with polyamines such as spermidine and spermine are strikingly similar to some toxins from spiders and predatory wasps. Many plants contain phenolic acid polyamine conjugates and there is some reliable information supporting their roles as plant defense chemicals. Eleven monoacylated compounds of diamines, triamines, tetraamines and oxa-polyamine amines were prepared in three to seven steps: 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 and 32. The synthesis proceeds through stepwise construction of the polyamine backbone (as in 62 and 72), followed by protection and deprotection steps of the amino functions. Desymmetrization of readily available and prepared symmetrical polyamines is a key step in the synthesis. The protecting groups employed were tert-butoxycarbonyl (BOC) and trifluoroacetyl (TFA) group which were removed under different conditions: acid and base respectively. Deprotection and refunctionalization of the polyamine reagent demonstrated the versatility of these systems for N-acylation.

Indenture - 1773

An indenture dated October 1, 1773 between Mary Willson (daughter of Andrew Willson) and Hill Carney and Sarah his wife and Mary their daughter. Mary "hath put herself and by this presents doth voluntarily and of her own free will and accord put herself Apprentice to Hill Carney Sarah his wife and Mary their daughter".

Indenture between Joseph Hamilton and Joseph Hart

Indenture of sale between Joseph Hamilton of London and Joseph Hart of Montgomery County. This is regarding Lot no. 25 in the 5th concession in the Township of Norwich in the County of Oxford, May 11, 1833.

Indenture between William Arnott and Elizabeth Arnott and Nathan Thomas Fitch

Indenture of mortgage between William Arnott and Elizabeth Arnott of Welland County to Nathan Thomas Fitch of Welland County for Lots numbered 37 and the south half of 40 and 41 in the village of Merritville - instrument no. 5400, September 12, 1836.

Indenture between Margaret Adams and Samuel DeVeaux Woodruff

Indenture of deed of land by way of quit-claim between Margaret Adams of St. Catharines and Samuel DeVeaux Woodruff of St. Catharines regarding parts of Lots no. 20 and 21 in the 5th and 6th Concessions in the Township of Grantham. This was registered in the Lincoln County Registry on January 21, 1875 - instrument no. 2053 and instrument no. 4819, January 20, 1875.

Indenture of bargain and sale between Walter Hamilton Dickson and Augusta Maria Dickson of Niagara to Jane Dickson (widow of Robert Dickson), Thomas Clark Street of Stamford and Edward Clarke Campbell of Niagara

Indenture of bargain and sale between Walter Hamilton Dickson and Augusta Maria Dickson of Niagara to Jane Dickson (widow of Robert Dickson), Thomas Clark Street of Stamford and Edward Clarke Campbell of Niagara for 150 acres for the south half of Lot no. 32 in the 7th concession and the north east quarter of Lot no. 22 in the 10th Concession of Dumphries. This was recorded in the County of Halton on the 29th day of January, 1849 in Folio 326, memorial 236, Jan. 12, 1849.

Supporting social-cognitive development in the elementary years: The role of executive function and self-regulation

Every day we make decisions that have repercussions. Sometimes the effects are immediate and intended; other times the effects might be unintended or might not be apparent for years. As parents or educators, part of our role is to support the development of children’s decision-making skills, helping them to develop patterns of adaptive decision-making that will serve them well in their current lives and into the future. Part of successful decision-making involves self-control, a system served by the brain’s executive functions (EF). This involves the ability to put aside immediate reactions and base decisions on a variety of important considerations. Social-cognitive development, the ongoing improvement of the ability to get along with others and to understand others’ emotions, expressions, motivations, and intents, relies, to a large degree, on the same EF systems. The current paper explores the interaction of these two factors (the role of EF in social-cognitive development), explores the research to determine the most effective approaches to improving both factors, and develops a handbook providing activities for educators to use while supporting the growth of both EF and social-cognitive skills. Results of a needs assessment reveal that the majority (59%) of educators surveyed had never used a social skills improvement program in their classrooms, while a full 95% believed that social skills are important or very important for a student’s academic success.

Niagara Regional Historical Council fonds, 1960-1989

The Lincoln County Historical Council began meeting December 17,1960 under the advisement of the Publicity, Planning and Development Committee of Lincoln County. The group was composed of three members appointed from each of the four existing historical societies: one member appointed from the executive of the Women’s Institute, one member from Lincoln County Council, the Deputy-Clerk and Treasurer of the County and a member from the Niagara Editorial Bureau. The Welland County Historical Council was soon formed after this along the same lines. In the early 1960’s the Lincoln and Welland County historical councils began work on an inventory of historic buildings with the intent to emphasize the historical significance of this area. The information gathered by volunteers and a professional photographer and an architect was used to present a “brief” to the federal government in 1962 and the provincial government in 1963. This brief, An Area of Historical Interest in the Counties of Lincoln and Welland, Ontario was published in 1962 and revised and distributed to schools and libraries in the area in 1965. The Ontario Buildings Inventory Project became a provincial initiative spearheaded by the Department of Public Records and Archives, a branch of the Department of Tourism and Information, ca. 1966. Volunteers collected and photographed buildings of historical interest in Lincoln and Welland counties. This information was recorded on standardized survey forms for every township in the Niagara region. Niagara Regional Historical Council was created with the merger of Lincoln County Historical Council and Welland County Historical Council, at the time of the formation of Niagara Regional Government in 1970. The first meeting of the new council was held January 1970.

John N. Jackson papers, 1960-1989, n.d.

John N. Jackson was born in Nottingham, England in 1926. He developed a passion for landforms and geography from his father, a high school math and science teacher who had studied geology. During the Second World War, he served in the British Navy. He received his BA from the University of Birmingham, and a PhD from the University of Manchester. After spending a year as a visiting professor at the University of British Columbia, he was hired in 1965 as the founding head of the Geography Department at Brock University. He taught at Brock for more than 25 years, immersing himself in the geography and history of the Niagara area. He became particularly interested in the history of the Welland Canals. He authored 20 books on various topics, including land use in Niagara, the history of St. Catharines, the Welland Canal, and railways in the Niagara Peninsula. He died in 2010, at the age of 84.

Summons - Shaw vs. Hoover et al. 1851

A summons to Henry Hoover of the Township of Thorold in the county of Welland, William Cowan of the Village of Dunville in the county of Haldimand, James Park and John H. Casper of the township of Thorold in the county of Welland.