Publication Date

2012-05-03

Availability

Open access

Embargo Period

2012-05-03

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PHD)

Department

Chemistry (Arts and Sciences)

Date of Defense

2012-04-12

First Committee Member

Burjor Captain

Second Committee Member

Carl D. Hoff

Third Committee Member

Rajeev Prabhakar

Fourth Committee Member

Priyamvada Rai

Abstract

The role of bulky tin ligands in the stabilization of transition metal complexes with electronic unsaturation has been studied to understand the mode of binding of small molecules at an unsaturated metal center. We were able to isolate electronically unsaturated Pt-Sn bimetallic complexes effective in the reversible activation of small molecules including CO, H2, C2H4, and NH3 at room temperature. We have examined the effect of the modification of ligands in Pt-Sn bimetallic complexes for the activation of small molecules and have observed that the Pt(SnBut3)2(CNBut)2 bimetallic complex reversibly activates hydrogen at room temperature both in the solid state and in solution. Similarly, we have also prepared bimetallic Pt-Sn complexes with an NHC carbine ligand which were also shown to activate hydrogen and alkenes reversibly. A bimetallic Fe-Sn cluster complex, Fe2 (µ-SnBut2)2(CO)8, was synthesized from the reaction of But3SnH with the Fe2(CO)9 and shown to be selective at activating the benzylic C-H bond of alkylaromatic solvent molecules. The new complexes containing tin have been characterized spectroscopically to gain an insight into the reaction mechanism involved in small molecule activation.

Keywords

bulky tin ligands; unsaturated metal complexes; bimetallic complexes; small molecule activation; reversible hydrogen activation; heterometallic cluster complexes; transition-tin metal complexes

Share

COinS