Diphosphine Ligand Substitution in H4Ru4(CO)12: X-ray Diffraction Structures and Reactivity Studies of the Diphosphine Substituted Cluster Products

Use of this thesis is restricted to the UNT Community. Off-campus users must log in to read.

Description

The tetraruthenium cluster H4Ru4(CO)12 has been studied for its reactivity with the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2, 4,5-bis (diphenylphosphino)-4-cyclopenten-1,3-dione, bis(diphenyphosphino)benzene and 1,8- bis(diphenyl phosphino)naphthalene under thermal, near-UV photolysis, and Me3NO-assisted activation. All three cluster activation methods promote loss of CO and furnish the anticipated substitution products that possess a chelating diphosphine ligand. Clusters 1, 2, 3 and 4 have been characterized in solution by IR and NMR spectroscopies, and these data are discussed with respect to the crystallographically determined structures for all new cluster compounds. The 31P NMR spectral data and the solid-state structures confirm the presence of a chelating diphosphine ... continued below

Creation Information

Kandala, Srikanth December 2006.

Context

This thesis is part of the collection entitled: UNT Theses and Dissertations and was provided by UNT Libraries to Digital Library, a digital repository hosted by the UNT Libraries. It has been viewed 108 times . More information about this thesis can be viewed below.

Who

People and organizations associated with either the creation of this thesis or its content.

Chair

Committee Member

Publisher

Rights Holder

For guidance see Citations, Rights, Re-Use.

  • Kandala, Srikanth

Provided By

UNT Libraries

Library facilities at the University of North Texas function as the nerve center for teaching and academic research. In addition to a major collection of electronic journals, books and databases, five campus facilities house just under six million cataloged holdings, including books, periodicals, maps, documents, microforms, audiovisual materials, music scores, full-text journals and books. A branch library is located at the University of North Texas Dallas Campus.

Contact Us

What

Descriptive information to help identify this thesis. Follow the links below to find similar items on the Digital Library.

Degree Information

Description

The tetraruthenium cluster H4Ru4(CO)12 has been studied for its reactivity with the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2, 4,5-bis (diphenylphosphino)-4-cyclopenten-1,3-dione, bis(diphenyphosphino)benzene and 1,8- bis(diphenyl phosphino)naphthalene under thermal, near-UV photolysis, and Me3NO-assisted activation. All three cluster activation methods promote loss of CO and furnish the anticipated substitution products that possess a chelating diphosphine ligand. Clusters 1, 2, 3 and 4 have been characterized in solution by IR and NMR spectroscopies, and these data are discussed with respect to the crystallographically determined structures for all new cluster compounds. The 31P NMR spectral data and the solid-state structures confirm the presence of a chelating diphosphine ligand in all four new clusters. Sealed NMR tubes containing clusters 1, 2, 3 and 4 were found to be exceeding stable towards near-UV light and temperatures up to ca. 100°C. The surprisingly robust behavior of the new clusters is contrasted with the related cluster Ru3(CO)10(bpcd) that undergoes fragmentation to the donor-acceptor compound Ru2(CO)6(bpcd) and the phosphido-bridged compound Ru2(CO)6 (µ-PPh2)[µ-C=C(PPh2)C(O)CH2C(O)] under mild conditions. The electrochemical properties have been investigated in the case of clusters 1 and 2 by cyclic voltammetry, and the findings are discussed with respect to the reported electrochemical data on the parent cluster H4Ru4(CO)12.

Subjects

Keywords

Library of Congress Subject Headings

Language

Identifier

Unique identifying numbers for this thesis in the Digital Library or other systems.

Collections

This thesis is part of the following collection of related materials.

UNT Theses and Dissertations

Theses and dissertations represent a wealth of scholarly and artistic content created by masters and doctoral students in the degree-seeking process. Some ETDs in this collection are restricted to use by the UNT community.

What responsibilities do I have when using this thesis?

When

Dates and time periods associated with this thesis.

Creation Date

  • December 2006

Added to The UNT Digital Library

  • May 5, 2008, 3:09 p.m.

Description Last Updated

  • Dec. 15, 2008, 5:14 p.m.

Usage Statistics

When was this thesis last used?

Yesterday: 0
Past 30 days: 1
Total Uses: 108

Interact With This Thesis

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Kandala, Srikanth. Diphosphine Ligand Substitution in H4Ru4(CO)12: X-ray Diffraction Structures and Reactivity Studies of the Diphosphine Substituted Cluster Products, thesis, December 2006; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc5410/: accessed April 29, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .