Date of Award

5-2016

Document Type

Thesis

Primary Advisor

Gregory Powell

Secondary Advisor

Cynthia Powell

Committee Reader

Perry Reeves

Abstract

New triosmium carbonyl complexes containing multiple bis(diphenylphosphino)methane (dppm) ligands were synthesized via reactions of Os3(CO)12 with excess dppm under microwave irradiation. The new complexes have been characterized by IR, NMR, mass spectrometry, and X-ray crystallography. Three of the four complexes produced, Os3(μ-H)2(CO)6(μ-dppm)[μ3-Ph2PCHP(C6H4)Ph] (2), Os3(CO)63-Ph2PCH2P(C6H4)Ph]2 (3), and Os3(μ-H)(CO)63-PhPCH2P(C6H4)Ph][μ3- PhPCH(C6H4)PPh] (4), contain two dppm ligands in a triosmium cluster, while the fourth, Os3(μ-H)(CO)5(dppm)[μ3-PhPCH2P(C6H4)Ph][μ3-PhPCH(C6H4)PPh] (5), contain three dppm ligands, the first of its kind. All of the new complexes contain at least one dppm ligand which underwent C–H and/or C–P bond activation. Complex 2 is a 48e cluster containing two dppm ligands, one intact and one that spans all three osmium sites through a phosphorous atom and the cyclometalated and ortho-metalated carbon atoms. Complex 3 in contrast, is a 46e cluster with two ortho-metalated dppm ligands. Complexes 4 and 5 are 50e clusters with similar metallic framework containing one cyclometalated dppm ligand and one ortho-metalated dppm ligand.

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Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.

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