Michael Hogue fonds

Michael H. [Henry] Hogue (1878-1963) was the son of Lemuel and Frances Hogue of Wainfleet Township, Welland County. In 1901 Michael Hogue was married to Margaret Case and they had five sons, William, Lemuel, Harry, Ross and Frank. In the 1911 Census of Canada he is residing in Welland and working as a blacksmith for Howard H. Lymburner. At Lymburner’s retirement, Hogue purchased the business and moved it from 15 Niagara Street, Welland to 12 Frazer Street, Welland. Mr. Hogue’s blacksmith activities included work with various industries in Welland including the expansion of blacksmithing work into the automobile industry. Mr. Hogue also worked for subcontractors Canadian Dredge & Dock and G.L. Campbell. These jobs included work related to the Welland Ship Canal in 1923. The business ceased operation in 1956.

Asymmetric hydrogenation of alkenes with cationic iridium(I) complexes of 2-phosphino-1-aminoferrocene ligands

Iridium complexes with bidentate P,N ligands represent a class of catalysts that significantly expand the application range of asymmetric hydrogenation. New substrate classes, for which there have previously been no suitable catalysts, can now be efficiently hydrogenated in high conversion and enantioselectivity. These substrates are often of synthetic importance, thus iridium catalysis represents a significant advance in the field of asymmetric catalysis. Planar chiral ferrocenyl aminophosphine ligands in which both heteroatoms were directly bound to the cyclopentadienyl ring were prepared by BF3-activated lithiationsubstitution in the presence of a chiral diamine in 49-59% yield and 75-85% enantiomeric excess. Some of these ligands were recrystallized to enantiomeric purity via ammonium fluoroborate salt formation of the phosphine sulfide. A crystal structure of one of these compounds was obtained and features an intramolecular hydrogen bond between the nitrogen, hydrogen, and sulfur atoms. Neutralization, followed by desulfurization, provided the free ligands in enantiomeric purity. Iridium complexes with these ligands were formed via reaction with [Ir(COD)Clh followed by anion exchange with NaBArF. These complexes were successfully applied in homogeneous hydrogenation of several prochiral substrates, providing products in up to 92% enantiomeric excess. Variation of the dimethyl amino group to a pyrrolidine group had a negative effect on the selectivity of hydrogenation. Variation of the substituents on phosphorus to bulkier ortho-tolyl groups had a positive effect, while variation to the more electron rich dicyclohexyl phosphine had a negative effect on selectivity.

Welland Canal Survey of Lands Michael and Jacob Silverthorn, 1834

Survey map and description of Michael and Jacob Silverthorn's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; line between Burger and Silverthorn's land, reservoir, wood land, road leading to Quaker settlement, line between Jacob and Michael Silverthorn's land. The deeds for both lands are dated September 25, 1834. Surveyor notes are seen in pencil on the map.

Hydrosilylation and hydroboration catalyzed by imido-hydride complexes of molybdenum (IV)

This thesis describes the synthesis, structural studies, stoichiometric and catalytic reactivity of novel Mo(IV) imido hydride complexes (Cp)(ArN)Mo(H)(PMe3) (1) and (Tp )(ArN)Mo(H)(PMe3) (2). Both 1 and 2 catalyze hydrosilylation of a variety of carbonyls. Detailed kinetic and DFT studies found that 1 reacts by an unexpected associative mechanism, which does not involve Si-H addition either to the imido group or the metal. Despite 1 being a d2 complex, its reaction with PhSiH3 proceeds via a a-bond metathesis mechanism giving the silyl derivative (Cp )(ArN)Mo(SiH2Ph)(PMe3). In the presence of BPh3 reaction of 1 with PhSiH3 results in formation of (Cp)(ArN)Mo(SiH2Ph)(H)2 and (Cp)(ArN)Mo(SiH2Ph)2(H), the first examples ofMo(VI) silyl hydrides. AI: 1 : 1 reaction between 2, PhSiD3 and carbonyl substrate established that hydrosilylation is not accompanied by deuterium incorporation into the hydride position of the catalyst, thus ruling out the conventional mechanism based on carbonyl insertion carbonyl. As 2 is nomeactive to both the silane and ketone, the only mechanistic alternative we are left with is that the metal center activates the carbonyl as a Lewis acid. The analogous nonhydride mechanism was observed for the catalysis by (ArN)Mo(H)(CI)(PMe3), (Ph3P)2(I)(O)Re(H)(OSiMe2Ph) and (PPh3CuH)6. Complex 2 also catalyzes hydroboration of carbonyls and nitriles. We report the first case of metal-catalyzed hydroboration of nitriles as well as hydroboration of carbonyls at very mild conditions. Conversion of carbonyl functions can be performed with high selectivities in the presence of nitrile groups. This thesis also reports the first case of the HlH exchange between H2 and Si-H of silanes mediated by Lewis acids such as Mo(IV) , Re(V) , Cu(I) , Zn(II) complexes, B(C6Fs)3 and BPh3.

Michael Hornyansky Fonds,

Michael Sands Hornyansky was the son of well-known artist, Nicholas Hornyansky and a cellist. He attended Oakwood Collegiate, Toronto; University College in Toronto and Merton College, Oxford where he was a Rhodes scholar. He won the Newdigate prize for poetry in 1951. Dr. Hornyansky taught English Language and Literature at Carleton University, Ottawa for 10 years before moving to Niagara in 1964. He was the founding chairman of the English Department of Brock University where he remained until his retirement in 1993. Some of his achievements include:The Golden Phoenix, a retelling of French Canadian folk tales and the publishing of papers on children’s literature and the discriminating use of the English language. He also reviewed poetry for the University of Toronto Quarterly. Michael Hornyansky died on May 14th, 2008 in Alberta at the age of 81. The annual Michael Hornyansky prize for creative writing was established at Brock University.

Understanding the Origin of Selectivity in the Asymmetric Lithiation Reaction of N-Heterocycles: A Theoretical Study

The natural abundance of the N-heterocycle containing compounds has pushed the synthetic community toward the invention of new synthetic methods that result in the structural diversity of N-heterocycles. Among this, is the efficient and highly selective diamine mediated asymmetric lithiation process. Amongst the diamine chiral ligands, (-)-sparterine, which is a naturally occurring alkaloid proved to be an efficient one. Many successful, good yielding and highly selective lithiation reactions have been accomplished with the mediation by this chiral diamine base. Although, there are some examples of experimental and theoretical mechanistic studies in the literature, there is a lack of detailed understanding as to how it exactly induces the chirality. In this thesis is described a systematic investigation of how (-)-sparteine influences the stereoselectivity in the course of asymmetric lithiation reaction. This led us to the establishment of the function of A-ring’s β-CH2 effect and D-ring effect. Consequently, the importance of the A-ring and D-ring portions of (-)-sparteine in the stereoselectivity is unraveled. Another part of this thesis deals with the asymmetric lithiation of BF3-activated N,N- dimethylaminoferrocene in the presence of (1R, 2R)-N1,N2-bis(3,3-dimethylbutyl)-N1,N2-dimethylcyclohexane-1,2-diamine ( a (R,R)-TMCDA surrogate) with i-PrLi. Computational findings were in full accord with the experimental observations. Subsequently, the theoretically provided insights into the mechanism of the reaction were exploited in computational design of a new ligand. Unfortunately, the outcome of this design was not experimentally robust and an updated approach towards a successful design was explained.

Photograph - Mr. & Mrs. Michael Henry (nee Almedie Mann)

A photograph of Mr. & Mrs. Michael Henry (nee. Almedie Mann) taken by G.F. Maitland, photographer, St. Paul Street, St. Catharines.

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.

Letter- Michael H. Wilson to Donald Ziraldo, 1993

A letter from Michael H. Wilson, Minister of Industry, Science and Technology and Minister of International Trade, dated 7 May, 1993. He discusses the achievements of Inniskillin in the "Vinitaly" wine exhibition. Wilson also remarks on the great accomplishments of Mr. Ziraldo as chairman of the Ontario Vintners Quality Alliance (VQA).

Letter - Michael D. Harris to Donald Ziraldo, 2000

A letter from Premier Mike Harris to Donald Ziraldo 15 June, 2000. The correspondence discusses the possibility of agricultural preserve in Niagara.

Letter - R.Michael Mondavi to Donald Ziraldo, 1997

A letter from R. Michael Mondavi of Robert Mondavi Winery congratulating Donald Ziraldo on the release of his book Anatomy of a Winery and thanking him for the copy he was sent. He comments on the beautiful images and compares the beauty of the photographs with the landscape of Napa Valley. 2 May, 1997

Photograph - Donald Ziraldo, Michael Budman, Ross Rebagliati & others in Aspen, CO

A photograph of five people, some are identifiable, such as Donald Ziraldo, Roots Co-founder Michael Budman and Ross Rebagliati, Canadian professional snowboarder and Olympic gold medal winner for Men's Snowboarding at the 1998 Winter Olympics. On the back it is noted that this is Aspen Colorado in 1998. This may relate to the 1998 Winter Games as two people in the picture are wearing the Roots hat designed for that event.

Diastereoselective Synthesis of Planar Chiral N-Substituted Ferrocenes Derived from Epimeric Imidazolones and their Application to Asymmetric Hydrogenation of Quinolines

This thesis describes the synthesis and use of an N-substituted ferrocene bearing a proline-derived chiral directing group and diastereoselective lithiation-electrophile quench of the pro-Sp hydrogen of the ferrocene to give planar chiral products in >95:5 dr. The auxiliary group is found to be stable to lithium bases of types RLi and R2NLi giving the same diastereoselectivity. The anti- epimer of the previously mentioned syn auxiliary induces lithiation of pro Rp rather than pro Sp hydrogen in >95:5 dr. Upon electrophile quench and elimination, the enantiomer of the syn-derived planar chiral imidazolone is obtained. Hence, this method provides a practical way to prepare planar chiral enantiomers in this series without the use of a more expensive D-proline derived starting material. The syn and anti epimers have β, γ-stereogenic centers and the origin of stereoselectivity in lithiation appears to be driven by the conformational bias exerted by the β-silyloxy moiety in each chiral auxiliary. In the thesis, this conclusion is supported using insensitivity of lithiation selectivity to the bulkiness of the base, comparison of enantiomers, deuteration experiments, nOe difference studies and computational modeling of the ground states and lithiation transition states for both substrates. The products are then converted to ligand precursors to make iridium and rhodium complexes. Among them, one of the cationic iridium complex is found to be effective in the asymmetric hydrogenation of 2-substituted quinolines with enantioselectivities up to 80% at pressures as low as 5 atm.

Letter to Henry Nelles from Michael Harris of the Perth Military Settlement

Letter to Henry Nelles from Michael Harris of the Perth Military Settlement (3 pages, handwritten). He is married to Mary Fanning, sister of Henry Nelles but is having marital troubles as he says he “may have to be on the lookout for another wife”. He thinks that his wife Mary may have departed for the United States, Apr. 6, 1821.

Letter to Henry Nelles from Michael Harris regarding estate problems

Letter to Henry Nelles from Michael Harris regarding estate problems (3 pages, handwritten with writing going in 2 directions on the last page), May 30, 1821.