Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/13963
Title: Protonation of η5-indenyl ruthenium hydride complexes (η5-C9H7)Ru(L2)H and η5-η6 haptotropic rearrangement. X-ray crystal structures of (η5-C9H7)Ru(dppm)H and [(η5-C9H8) Ru(dppp)H]+
Authors: Hung, MY
Ng, SM
Zhou, Z
Lau, CP
Jia, G
Issue Date: 2000
Publisher: American Chemical Society
Source: Organometallics, 2000, v. 19, no. 18, p. 3692-3699 How to cite?
Journal: Organometallics 
Abstract: Protonation of indenyl complexes (η5-C9H7)Ru(dppm)H and (η5-C9H7)Ru(PPh3)2H with CF3-SO3H or HBF4·Et2O at -60°C gives the η2-dihydrogen complex [(η5-C9H7)Ru(dppm)(H2)]+ and the dihydrate [(η5-C9H7)Ru(PPh3)2H2]+, respectively. Upon warming to room temperature, proton shift from the η2-H2 ligand of the former to the indenyl ligand and subsequent migration of the metal fragment from the five-membered ring to the six-membered ring of the indene ligand results in the formation of the η6-indene complex [(η6-C9H8)Ru(dppm)H]+. The PPh3 analogue [(η6-C9H8)Ru(PPh3)2H]+ is formed in a similar fashion, but in this case, the proton shift is from Ru-H to the indenyl ligand. Low-temperature acidification of (η5-C9H7)Ru(dppe)H and (η5-C9H7)Ru (dppp)H yield mixtures of η2-dihydrogen complex and dihydride in both cases. Similar to the dppm and PPh3 analogues, η6-indene complexes [(η6-C9H8)Ru(dppe)H]+ and [(η6-C9H8)Ru(dppp)H]+ are generated upon warming solutions of the η2-dihydrogen complex/dihydride mixtures to room temperature. In the dppp system, the η5 → η6 haptotropic rearrangement only occurs after the η2-dihydrogen complex → dihydride tautomerization is nearly completed, whereas in the dppe system the two processes seem to occur simultaneously. The parent hydride complexes (η5-C9H7)Ru(L2)H can be regenerated upon deprotonation of the η6-indene complexes with Et3N. Crystal structures of (η5-C9H7)Ru(dppm)H and [(η6-C9H8)Ru(dppp)H]+ have been determined by X-ray crystallography; both complexes have three-legged piano-stool structures.
URI: http://hdl.handle.net/10397/13963
ISSN: 0276-7333
EISSN: 1520-6041
DOI: 10.1021/om000266e
Appears in Collections:Journal/Magazine Article

Access
View full-text via PolyU eLinks SFX Query
Show full item record

SCOPUSTM   
Citations

12
Last Week
0
Last month
0
Citations as of Aug 11, 2017

WEB OF SCIENCETM
Citations

12
Last Week
0
Last month
0
Citations as of Aug 14, 2017

Page view(s)

29
Last Week
1
Last month
Checked on Aug 13, 2017

Google ScholarTM

Check

Altmetric



Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.