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Acetylide Participation in Ligand Substitution and P−C Bond Cleavage in the Reaction between HRu<INF>3</INF>(CO)<INF>9</INF>(μ<INF>3</INF>,η<SUP>2</SUP>,η<SUP>2</SUP>,η<SUP>1</SUP>-C&tbd1;CPh) and 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Syntheses and X-ray Structures of HRu<INF>3</INF>(CO)<INF>7</INF>[μ<INF>3</INF>,η<SUP>2</SUP>,η<SUP>2</SUP>,η<SUP>1</SUP>,η<SUP>1</SUP>,η<SUP>1</SUP>-Ph<INF>2</INF>PC&dbd;CC(O)CH<INF>2</INF>C(O)PPh<INF>2</INF>C&dbd;CPh] and Ru<INF>3</INF>(CO)<INF>7</INF>(μ,

Authors :
Bott, S. G.
Shen, H.
Senter, R. A.
Richmond, M. G.
Source :
Organometallics; April 2003, Vol. 22 Issue: 9 p1953-1959, 7p
Publication Year :
2003

Abstract

The triruthenium cluster HRu&lt;INF&gt;3&lt;/INF&gt;(CO)&lt;INF&gt;9&lt;/INF&gt;(μ&lt;INF&gt;3&lt;/INF&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-C&amp;tbd1;CPh) (&lt;BO&gt;1&lt;/BO&gt;) reacts with the diphosphine ligand bpcd in the presence of Me&lt;INF&gt;3&lt;/INF&gt;NO to afford the new cluster compounds HRu&lt;INF&gt;3&lt;/INF&gt;(CO)&lt;INF&gt;7&lt;/INF&gt;(bpcd)(μ&lt;INF&gt;3&lt;/INF&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-C&amp;tbd1;CPh) (&lt;BO&gt;2&lt;/BO&gt;) and &lt;ETIEBAR ID=&quot;om0300169a10003&quot;&gt;HRu&lt;INF&gt;3&lt;/INF&gt;(CO)&lt;INF&gt;7&lt;/INF&gt;[μ&lt;INF&gt;3&lt;/INF&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-Ph&lt;INF&gt;2&lt;/INF&gt;P&lt;TIEBAR NUM=&quot;om030016900000&quot;&gt;C&amp;dbd;CC(O)CH&lt;INF&gt;2&lt;/INF&gt;&lt;/TIEBAR&gt;C(O)PPh&lt;INF&gt;2&lt;/INF&gt;C&amp;dbd;CPh]&lt;/ETIEBAR&gt; (&lt;BO&gt;3&lt;/BO&gt;). Cluster &lt;BO&gt;2&lt;/BO&gt; is the sole product from the controlled thermolysis of &lt;BO&gt;1&lt;/BO&gt; with bpcd. Both &lt;BO&gt;2&lt;/BO&gt; and &lt;BO&gt;3&lt;/BO&gt; have been isolated and characterized in solution by IR and NMR (&lt;SUP&gt;1&lt;/SUP&gt;H and &lt;SUP&gt;31&lt;/SUP&gt;P) spectroscopies, and by X-ray crystallography in the case of the latter cluster. The bpcd ligand in &lt;BO&gt;2&lt;/BO&gt; chelates to the ruthenium center that is σ bound by the acetylide ligand, and in the zwitterionic compound &lt;BO&gt;3&lt;/BO&gt; one of the PPh&lt;INF&gt;2&lt;/INF&gt; moieties of the bpcd ligand coordinates to a hydride-bridged ruthenium atom while the other PPh&lt;INF&gt;2&lt;/INF&gt; group exists as a phosphonium center due to attack on the acetylide C&lt;INF&gt;α&lt;/INF&gt; carbon. Whereas &lt;BO&gt;3&lt;/BO&gt; slowly decomposes in solution at elevated temperatures, cluster &lt;BO&gt;2&lt;/BO&gt; was found to undergo a clean conversion to the new cluster &lt;ETIEBAR ID=&quot;om0300169a10004&quot;&gt;Ru&lt;INF&gt;3&lt;/INF&gt;(CO)&lt;INF&gt;7&lt;/INF&gt;(μ,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-PhC&amp;dbd;CHPh)[μ&lt;INF&gt;2&lt;/INF&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-PPh&lt;TIEBAR NUM=&quot;om030016900000&quot;&gt;C&amp;dbd;CC(O)CH&lt;INF&gt;2&lt;/INF&gt;&lt;/TIEBAR&gt;C(O)PPh&lt;INF&gt;2&lt;/INF&gt;]&lt;/ETIEBAR&gt; (&lt;BO&gt;4&lt;/BO&gt;). The bridging alkenyl ligand in &lt;BO&gt;4&lt;/BO&gt; results from the formal cleavage of one of the P−Ph bonds of the bpcd ligand, followed by the concomitant coupling of the phenyl and hydride groups with the acetylide ligand. Cluster &lt;BO&gt;4&lt;/BO&gt; has been fully characterized in solution and the solid-state structure established by X-ray analysis. NMR data are presented from a labeling study employing HRu&lt;INF&gt;3&lt;/INF&gt;(CO)&lt;INF&gt;7&lt;/INF&gt;(bpcd)(μ&lt;INF&gt;3&lt;/INF&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-C&amp;tbd1;Ctol-p) that shows that the hydrogen in the μ,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-RC&amp;dbd;CHR‘ moiety of &lt;ETIEBAR ID=&quot;om0300169a10005&quot;&gt;Ru&lt;INF&gt;3&lt;/INF&gt;(CO)&lt;INF&gt;7&lt;/INF&gt;(μ,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-RC&amp;dbd;CHR‘)[μ&lt;INF&gt;2&lt;/INF&gt;,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-PPh&lt;TIEBAR NUM=&quot;om030016900000&quot;&gt;C&amp;dbd;CC(O)CH&lt;INF&gt;2&lt;/INF&gt;&lt;/TIEBAR&gt;C(O)PPh&lt;INF&gt;2&lt;/INF&gt;]&lt;/ETIEBAR&gt; is distributed between both the phenyl and tol-p groups. The scrambling of the alkenyl hydrogen between the phenyl- and tol-p-substituted carbon atoms in the μ,η&lt;SUP&gt;2&lt;/SUP&gt;,η&lt;SUP&gt;1&lt;/SUP&gt;-RC&amp;dbd;CHR‘ moiety suggests that hydride transfer from the triruthenium frame occurs via a transient cluster compound that possesses a coordinated PhC&amp;tbd1;Ctol-p ligand.

Details

Language :
English
ISSN :
02767333 and 15206041
Volume :
22
Issue :
9
Database :
Supplemental Index
Journal :
Organometallics
Publication Type :
Periodical
Accession number :
ejs4497334

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