Publication Date

2009-03-06

Availability

Open access

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PHD)

Department

Chemistry (Arts and Sciences)

Date of Defense

2009-02-17

First Committee Member

Steven P. Nolan - Committee Member

Second Committee Member

Burjor Captain - Committee Member

Third Committee Member

Angel Kaifer - Committee Member

Fourth Committee Member

Carl D. Hoff - Mentor

Abstract

The reactivities of several electron rich, low-valent group 6 complexes with a series of N-donor ligands were explored in order to gain information about the nature of M-N binding. Reactions of trimethylsilyl diazomethane (N=N=CHSiMe3) and 1-adamntyl azide (N=N=N-Ad) with the organometallic complexes [Cr(CO)3(C5R5)]2 (R = H, Me) and HMo(CO)3(C5R5) (R = H, CH3) were studied from both a kinetic and thermodynamic aspect. Ultimately, this information was used to propose plausible mechanisms by which the reactions take place. Furthermore, reactions of M(PiPr3)2(CO)3 (M = Mo, W; iPr = isopropyl) with N2, trimethylsilyl diazomethane, 1-adamantyl azide, a series of nitriles, and a choice group of N-heterocyclic compounds were studied. The use of the coordinatively unsaturated but sterically hindered M(PiPr3)2(CO)3 complex was used to evaluate the importance of sigma and pi bonding in these complexes.

Keywords

Nitrogen; Heat Of Binding; Diazo; Azide; Nitrile; Molybdenum; Chromium

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