Mononuclear and dinuclear complexes with a [Ru(tBu2PCH2CH2PtBu2)(CO)] core
- 17 December 2004
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Dalton Transactions
- No. 3,p. 588-597
- https://doi.org/10.1039/b415812a
Abstract
Thermolysis of solid [Ru(dtbpe)(CO)2Cl2] (2, dtbpe = tBu2PCH2CH2PtBu2) under vacuum affords the five-coordinate complex [Ru(dtbpe)(CO)Cl2] (4), which was shown by X-ray crystallography to contain a weak remote agostic interaction. In solution, 4 can be readily trapped by CO, CH3CN or water to give [Ru(dtbpe)(CO)(L)Cl2] (L = CO, 2; L = CH3CN, 6; L = H2O, 7). Reaction of 4 with AgOTf/H2O yields the tris-aqua complex [Ru(dtbpe)(CO)(H2O)3](OTf)2 (8), which has been structurally characterised and probed in solution by pulsed-gradient spin echo (PGSE) NMR spectroscopy. The water ligands in 8 are labile and easily substituted to give [Ru(dtbpe)(CO)(NCCH3)3](OTf)2 (10) and [Ru(dtbpe)(CO)(DMSO)3](OTf)2 (11). In the presence of CO, the tris-aqua complex undergoes water–gas shift chemistry with formation of the cationic hydride species [Ru(dtbpe)(CO)3H](OTf) (12) and CO2. X-Ray crystal structures of complexes 2, 4, 6, 8 and 11–12 are reported along with those for [{Ru(dtbpe)(CO)}2(µ-Cl)2(µ-OTf)](OTf) (3), [{Ru(dtbpe)(CO)}2(µ-Cl)3][Ru(dtbpe)(CO)Cl3] (5) and [Ru(dtbpe)(CO)(H2O)2(OTf)](OTf) (9).Keywords
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