Please use this identifier to cite or link to this item: http://scholarbank.nus.edu.sg/handle/10635/15505
Title: Reactions of triosmium carbonyl clusters with 1,1,1,-tris-(Diphenylphosphinomethyl)ethane
Authors: SANJIV KUMAR YADAV
Keywords: Osmium, Triphos, 2-quinolinethiol
Issue Date: 16-Aug-2006
Source: SANJIV KUMAR YADAV (2006-08-16). Reactions of triosmium carbonyl clusters with 1,1,1,-tris-(Diphenylphosphinomethyl)ethane. ScholarBank@NUS Repository.
Abstract: The reaction of 1,1,1-tris-(diphenylphosphinomethyl)ethane (Triphos) with [Os3(CO)11(NCMe) in toluene afforded two products: monosubstituted trinuclear cluster [Os3(CO)11(PPh2CH2)3CCH3], Cluster 1 and disubstituted bridging cluster [Os3(CO)8{A?-I?2-(PPh2CH2)3CCH3}], Cluster 2, where we observed the bonding of an uncoordinated phosphorus atom of Cluster 1 with another osmium atom by the displacement of a labile carbonyl group. Similarly [Os3(CO)10(A?-H)2] reacts with Triphos at 80 oC in THF to give an orthometallated and phosphorous bridged cluster [Os3(CO)7(A?-H)2(A?-PPh)Ph3P2C6H4)(CH2)3CCH3], Cluster 3. The reaction at 100 oC gave, apart from Cluster 3, a phosphorous-bridged cluster without orthometallation [Os3(CO)8(A?-H)(PPh2CH2)2(PPh2CH2)CCH3].0.5CH2Cl2], Cluster 4. Cluster 4 showed phosphorous and hydrido bridging to a metal-metal vector which affected the M-M bond lengths. Crystal diffraction studies of the product of the reaction at room temperature in dichloromethane showed two molecules in the unit cell, which were analysed to be the orthometallated and hydrido-bridged cluster [Os3(CO)7(I?-H(P2Ph2CH2)2PC6H4CCH3][Os3(CO)7(I?-H)(P2Ph2CH2)2PC6H4CCH3], Cluster 5. We have also begun preliminary studies of the reaction of 2-quinolinethiol with [Os3(CO)10(NCMe)2] at 100 oC, whereby the product demonstrated the simultaneous bridging of sulfur and hydrido ligands to a metal-metal vector in [Os3(CO)10(A?-H)(A?-S)C9H6N], Cluster 6. However in this case, we have observed that the metal-metal bond length was slightly shortened. All clusters have been established by X-ray crystallography and characterized by elemental analysis and spectroscopic methods (1H, 31P NMR, IR and MS).
URI: http://scholarbank.nus.edu.sg/handle/10635/15505
Appears in Collections:Master's Theses (Open)

Show full item record
Files in This Item:
File Description SizeFormatAccess SettingsVersion 
Chapters 1- 4.pdf919.13 kBAdobe PDF

OPEN

NoneView/Download
Appendix.pdf47.3 kBAdobe PDF

OPEN

NoneView/Download
1_Acknowledgement i.pdf10.19 kBAdobe PDF

OPEN

NoneView/Download
2_Table of Contents_ii-iii.pdf74.5 kBAdobe PDF

OPEN

NoneView/Download
3_Summary iv-v.pdf74.11 kBAdobe PDF

OPEN

NoneView/Download
4_Abbreviations List_vi.pdf56.7 kBAdobe PDF

OPEN

NoneView/Download
5_List of Compounds Obtained vii_NEW.pdf33.2 kBAdobe PDF

OPEN

NoneView/Download
Front page_Two.pdf13.59 kBAdobe PDF

OPEN

NoneView/Download

Page view(s)

235
checked on Dec 11, 2017

Download(s)

1,360
checked on Dec 11, 2017

Google ScholarTM

Check


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