Activation of hydrogen and related small molecules by the unsaturated cluster complex PtOs₃(CO)₇(PBu₃^t)(-PBu₂^t)(4-CHCMeCH) Academic Article

abstract

• Reactions of the unsaturated mixed metal cluster complex PtOs 3(CO)7(PBut3)(4- CHCMeCH), 1, with hydrogen, HGePh3, and PhC2H have been investigated. Compound 1 reacts reversibly with hydrogen at room temperature to yield the dihydrido complex PtOs3(CO)7(PBu t3)(-PBut2)(4- CHC-MeCH)(-H)(H), 2. A computational analysis shows that the hydrogen addition occurs by oxidative addition at the electronically unsaturated platinum atom and passes through two unstable intermediates before giving the final product 2. Compound 1 reacts with HGePh3 at the Ge-H bond to form the complex PtOs3(CO)7(PBut3)(- PBut2)(4-CHCMeCH)(GePh3)(-H) , 3, but in this reaction the HGePh3 addition occurred at one of the osmium atoms and a CO ligand was shifted to the platinum atom. Compound 1 reacts with PhC2H by loss of the platinum atom and the PBut3 ligand to give the compound Os3(CO)7(- PBut2)[3-5-CHCMeC(H)CCPhH], 4. In the process, the PhC2H molecule became bonded to the CHCMeCH ligand in 1 and its hydrogen atom was shifted to the phenyl-substituted carbon atom to form a triply bridging CHCMeC(H)CCPhH ligand. All of the products were characterized by single-crystal X-ray diffraction analyses. 2008 American Chemical Society.

authors

• Hall, Michael

published proceedings

• ORGANOMETALLICS

author list (cited authors)

• Adams, R. D., Boswell, E. M., Hall, M. B., & Yang, X.

citation count

• 17

complete list of authors

• Adams, Richard D||Boswell, Erin M||Hall, Michael B||Yang, Xinzheng

publication date

• October 2008

publisher

• American Chemical Society (ACS)  Publisher

published in

• Organometallics  Journal

keywords

• 34 Chemical Sciences
• 3402 Inorganic Chemistry

Digital Object Identifier (DOI)

• 10.1021/om800467v

start page

• 4938

end page

• 4947

volume

• 27

issue

• 19

URL

• http://dx.doi.org/10.1021/om800467v