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.

Macroeconomic News and LOB in Foreign Exchange ECN Market

We investigate the macroeconomic news effect on the dynamics of the limit order books (LOB) for euro-dollar ECN market in different economic states between Jan. 2006 to Dec. 2009. Using a VAR-STR model on the news surprise, pure news, aggregated good and bad news, we show that news effects on the LOB dynamics vary in different states of economy. The LOB dynamics are measured by depth, spread, slope and volatility. In contract to slope and volatility, depth and spread strongly respond to news surprise and pure news during recession and expansion. These characteristics are more affected by aggregated good and bad news during expansion. News effects are robust to alternative characteristic measures, the different sides of the LOB and the different levels in the LOB.

Camp Niagara Field Site States Forms from July to October 1916

A set of forms which was held together by a string. The title page is brittle and crumbling. Each page is dated and signed either by the Colonel or Lieutenant Colonel A.A.G. [Assistand Adjutant General] Niagara.

Indenture between Alfred Sanderson Woodruff and the United States Trust Company of New York

Indenture between Alfred Sanderson Woodruff and the United States Trust Company of New York. The proceeds would be paid to his estate for his successors. January 12, 1894.

Indenture between Hamilton Killaly Woodruff and the United States Trust Company of New York

Indenture between Hamilton Killaly Woodruff and the United States Trust Company of New York. The proceeds would be paid to his successors. (This is a handwritten copy)

Indenture between Hamilton Killaly Woodruff and the United States Trust Company of New York (3rd Trust Deed)

Indenture between Hamilton Killaly Woodruff and the United States Trust Company of New York. This is listed as the 3rd trust deed. The proceeds would be paid to successors (2 copies). Most of the first page of copy no. 2 is torn away which does affect the text. These 2 documents are in an envelope marked "vouchers", June 20, 1899.

Declaration from John Brown, culler who states that there are 1167 pieces which equal 75704 cubic feet of timber to be culled

Declaration from John Brown, culler who states that there are 1167 pieces which equal 75704 cubic feet of timber to be culled, April 9, 1878.

Letter with the salutation “Dear Sir” It is signed by John I. Mackenzie in which he states that he got the Globe to publish a letter about the Long Point expats which had been sent to the Ottawa Times

Letter with the salutation “Dear Sir” It is signed by John I. Mackenzie in which he states that he got the Globe to publish a letter about the Long Point expats which had been sent to the Ottawa Times. Most of the handwriting is illegible, Oct. 26, 1870.

Letter to W.D. Woodruff from Henry E. Ahern of United States Trust Company of New York

Letter to W.D. Woodruff from Henry E. Ahern of United States Trust Company of New York (1 page, printed) which was sent with a cheque for $2,106 in trust for his account. This is accompanied by an envelope addressed to the trust company, a balance sheet and a receipt, July 14, 1908.

Letter to W.D. Woodruff from Henry E. Ahern of United States Trust Company of New York

Letter to W.D. Woodruff from Henry E. Ahern of United States Trust Company of New York (1 page, printed) which was sent with a cheque for $560.63 in trust for his account. This is accompanied by an envelope addressed to Mr. Woodruff, a balance sheet and a receipt, Oct.10, 1908.

Letter to Mrs. Maria DeV. Haynes from Henry Ahern of the United States Trust Company of New York

Letter to Mrs. Maria DeV. Haynes from Henry Ahern of the United States Trust Company of New York (1 page, printed) stating that the funding of bonds has been paid, Jan. 4, 1909.

Letter to Mr. W. D. Woodruff from Henry Ahern of the United States Trust Company of New York

Letter to Mr. W. D. Woodruff from Henry Ahern of the United States Trust Company of New York (1 page, printed) stating that the funding of bonds has been paid. This is accompanied by an envelope addressed to Mr. Woodruff, a balance sheet and a receipt, Jan. 4, 1909.

Letter to Mr. W. D. Woodruff from Henry Ahern of the United States Trust Company of New York

Letter to Mr. W. D. Woodruff from Henry Ahern of the United States Trust Company of New York (1 page, printed) which was sent with a cheque for $2,925. This is accompanied by an envelope addressed to the trust company, a balance sheet and a receipt, Jan. 11, 1909.

Letter to Mr. W. D. Woodruff from Henry Ahern of the United States Trust Company of New York

Letter to Mr. W. D. Woodruff from Henry Ahern of the United States Trust Company of New York (1 page, printed) which was sent with a cheque for $410.41. This is accompanied by an envelope addressed to the trust company, a balance sheet and a receipt, Jan. 21, 1909.

Receipt sent to Mr. Welland D. Woodruff from the United States Trust Company of New York

Receipt sent to Mr. Welland D. Woodruff from the United States Trust Company of New York, [this receipt is not accompanied by a letter, but belongs in this file with the other trust company items], Apr. 5, 1909.