Dr. Bruce R. Whittlesey

Principal Research Interests

• Organometallic Chemistry
• Transition Metal / Group 13 Complexes
• Electronic Materials

Our research involves the synthesis of new transition metal compounds in which two very different metal centers are bound together. Current work centers on two major areas of investigation. The first is the study of metal clusters in which transition metal carbonyl fragments are attached by metal-metal bonds to transition metal atoms bound only to donor ligands such as tetrahydrofuran that have no p-acid capabilities. These species can be viewed as having classical "Werner-type" metal centers bonded to low-valent "organometallic" transition metals. Examples include [Mn][Mn7(THF)6(CO)12]2, {m-Mn(THF)2} [Mn(CO)5]2, and {m-Mn(THF)2]2Fe2(CO)8 (THF = tetrahydrofuran). All of the clusters isolated thus far are paramagnetic, and these are the only structurally-characterized compounds of this type in which all of the metals have open d-orbital subshells. We have proposed the term "xenophilic" metal cluster for this new class of compounds (from the Greek "xenos", meaning foreigner or stranger, and "philos", meaning loving). Current investigations are focused on the magnetic and spectroscopic properties of the clusters as well as the study of their reactivity and the preparation of new species.



The second area of study involves the preparation and reactivity of mixed-metal complexes in which transition metals are attached to Group 13 elements (B, Al, Ga, In, Tl). These compounds are then examined to better understand the bonding between the transition metal and the Group 13 element as well as to explore the possibility of their development as catalysts for organic synthesis and as precursors for the preparation of new inorganic materials. A number of important industrial processes utilize transition metal compounds and Lewis acids as cocatalysts (e.g. the Dupont process for preparing adiponitrile), and it has been shown that coordination of a Lewis acid to a reactant molecule can greatly enhance its ability to insert into transition metal-carbon bonds. One of the major goals of this research is to prepare catalysts in which the Lewis acid site, in the form of a Group 13 element, is attached directly to the transition metal rather than existing as a separate species in solution.

Representative Publications

• "Terminal Coordination of a Gallium(I) Species to a Transition Metal. Syntheses and Crystal Structures of Ru{GaCl(THF)2}{GaCl2(THF)}2(CO)3.0.5 THF and Ru2 {GaCl2(THF)}2(CO)8." Harakas, G.N.; Whittlesey, B.R., Inorg. Chem.1997, 36, 2704-2707.
• "Xenophilic Metal Clusters: Preparation and Crystal Structure of {m-Mn(THF)2}2Fe2(CO)8 (THF = tetra-hydrofuran)." Harakas, G.N.; Whittlesey, B.R. J. Am. Chem. Soc.1996, 118, 4210-4211.
• "An Unusual Transition Metal Cluster Containing a Seven Metal Atom Plane. Syntheses and Crystal Structures of [Mn][Mn7(THF)6(CO)12]2, Mn3(THF)2(CO)10, and [Mn(THF)6][Mn(CO)5]2(THF = tetrahydrofuran)." Kong, G.; Harakas, G.N.; Whittlesey, B.R. J. Am. Chem. Soc. 1995, 117, 3502-3509.
• "Preparation of [K] [In{Fe2(CO)8}2] (THF) and Fe2{m-InCl(THF)}2(CO)8 (THF tetrahydrofuran)" Lin, C.-C.; Kong, G.; Cho, C.; Whittlesey, B.R. Inorg. Chem.1993, 32, 2705.
• "Preparation and Crystal Structure of Ru3(m -Cl)2(THF)2(CO)8 (THF = Tetrahydrofuran)" Cho, H.; Whittlesey, B.R. Inorg. Chem.1993, 32, 3789.