Department of Chemistry

Andrew W. Holland

Associate Professor of Chemistry

Postdoctoral Studies, Heterogenous Catalysis, University of California, Berkeley – 2002-2004

Ph.D. Organometallic Chemistry, University of California, Berkeley – 2002

Research area: Organometallic Chemistry, Inorganic Chemistry

Student experience required for research: Chem 111, Chem 112, enrolled in Chem 301

Student experience gained from research: Synthetic methods, mechanistic methods, air-sensitive techniques, NMR.

Ideal preparation for: Graduate school in chemistry; petrochemical, specialty, and pharmaceutical chemical industries.

Research Description

1) Basic Late Metal Complexes in Catalysis

Anionic heteroatom ligands on electron-rich late metal centers may serve both basic and nucleophilic functions, but are frequently too high in relative energy to be regenerated cleanly in catalytic systems. We are interested in exploring, from a mechanistic inorganic perspective, scenarios that might overcome that problem to enable new bond activation and formation reactivity. Specifically, we aim to use chelating nitrogen ligands to produce strongly basic catalysts that can heterolytically activate H-X substrates to yield nucleophilic M-X species. We explore this idea through the preparation and study of new transition metal complexes.

Figure 1

2) Microwave Heating in Organometallic Chemistry

Microwave heating has proved to be a powerful tool in the synthesis of ligands, and we are currently exploring the potential and origins of the apparent acceleration associated with the technique. This work includes both practical application of microwaves to the syntheses of ligands and their complexes, and investigation of the kinetic changes (or lack thereof) induced by microwave heating.

Figure 2 Figure 3

3) New Approaches to Inorganic Materials Synthesis

The synthesis of inorganic materials has historically been approached largely from an entirely empirical perspective, but rational synthesis using well-defined solution phase techniques and molecular precursors has shown promise as an approach to targeting specific surface structures, particle sizes, and other properties. We are currently exploring the preparation of novel molecular precursors for nanoparticles with photovoltaic applications.

Journal Publications

"Synthesis and Reactivity of Sterically-Hindered Amido-Phosphine Complexes of Rhodium and Iridium." K. R. Seipel, K. L. Myers, M. Nguyen, B. B. Twamley, A. W. Holland, Inorg. Chem., manuscript in preparation.

"Kinetics of Reductive Elimination from Pt(IV) as a Probe for Non-Thermal Microwave Effects." C. Lombard, K. L. Myers, Z. H. Platt, A. W. Holland. Organometallics, submitted.

"Microwave-Assisted Synthesis of Phenylene-Bridged Amino-Phosphine Ligands: Acceleration of N-Arylation and Aryl Fluoride Phosphorylation Reactions." K. R. Seipel, Z. H. Platt, M. Nguyen, A. W. Holland. J. Org. Chem. 73, 4291-4294, 2008.

"New Fe/SiO2 Materials Prepared Using Molecular Precursors: Synthesis, Characterization, and Catalysis." A. W. Holland, G. T. Li, Ahmed M. Shahin, G J. Long, A. T. Bell, T. D. Tilley. J. Catal. 235-1, 150-163, 2005.

"Effects of Phosphine Chelation on the Reactivity of Monomeric Parent Amido Complexes: Synthesis and Reactivity of Such a Complex Bearing Monodentate Ligands," A.W. Holland, R.G. Bergman, J. Am. Chem. Soc. 124, 14684-14695, 2002.

"Thermal Reactivity of Group 9 Transition Metal Pinacolate Complexes: Heterocumulene Cleavage and C-O Bond Formation," A.W. Holland, R.G. Bergman, Inorg. Chim. Acta. 341, 99-106 (special issue, invited paper), 2002.

"Heterocumulene Metathesis by Iridium Guanidinate and Ureylene Complexes: Active Catalysis Involving Reversible Insertion to Form 6-Membered Metallacycles," A.W. Holland, R.G. Bergman, J. Am. Chem. Soc., 124, 9010-9011, 2002.

"Regiocontrol of Cyclometallation in a P4Ru(II) System. Unusual Base-Induced Metallation Within a Chelate Ring Versus Activation of a Methyl Group," A.W. Holland, R.G. Bergman, Organometallics, 21, 2149-52, 2002.

"Formation, Reactivity, and Properties of Non-Dative Late Transition Metal-Oxygen and -Nitrogen Bonds," J.R. Fulton, A.W. Holland, D.J. Fox, R.G. Bergman, Acc. Chem. Res., 35, 44-53, 2002.

"Photochemical Reactivity of Group 9 Metal Pinacolate Complexes," A.W. Holland, D.S. Glueck, R.G. Bergman, Organometallics, 20, 2250-2261, 2001.

"Direct Observation of C-O Reductive Elimination From Pt(IV)," B.S. Williams, A.W. Holland, K.I. Goldberg, J. Am. Chem. Soc., 121, 252-253, 1999.


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