Synthesis, characterisation and natural abundance Os-187 NMR spectroscopy of hydride bridged triosmium clusters with chiral diphosphine ligands
(2006) In Inorganica Chimica Acta 359(3). p.926-937- Abstract
- Treatment of [Os-3(mu-H)(2)(CO)(10)] with the chiral diphosphines BINAP, tolBINAP [(R)-2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl], DIOP [(4R,5R)-(-)-O-isopropenylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino) butane] affords [Os-3(mu-H)(2)(CO)(8)(mu-L)] (L = BINAP (1), tolBINAP (2), DIOP (4)) in high yield. The X-ray structures for 1, 2 and 4 are reported, and structural and spectroscopic comparisons are made between these clusters and [Os-3(mu-H)(2)(CO)(8)(mu-L)] (L = dppm (5), dppe (6), dppp (7)) which were synthesised similarly. Compounds 5 to 7 were previously synthesised by hydrogenation of 1,2-[OS3(CO)(10)(mu-L)] but the route from [Os(mu-H)(2)(CO)(10)] is preferable. The H-bridged Os center dot center dot Os distances are... (More)
- Treatment of [Os-3(mu-H)(2)(CO)(10)] with the chiral diphosphines BINAP, tolBINAP [(R)-2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl], DIOP [(4R,5R)-(-)-O-isopropenylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino) butane] affords [Os-3(mu-H)(2)(CO)(8)(mu-L)] (L = BINAP (1), tolBINAP (2), DIOP (4)) in high yield. The X-ray structures for 1, 2 and 4 are reported, and structural and spectroscopic comparisons are made between these clusters and [Os-3(mu-H)(2)(CO)(8)(mu-L)] (L = dppm (5), dppe (6), dppp (7)) which were synthesised similarly. Compounds 5 to 7 were previously synthesised by hydrogenation of 1,2-[OS3(CO)(10)(mu-L)] but the route from [Os(mu-H)(2)(CO)(10)] is preferable. The H-bridged Os center dot center dot Os distances are similar in 1, 2 and 4 indicating that these species are formally unsaturated 46-electron clusters. The P center dot center dot center dot P distances vary from 4.24 to 4.30 angstrom in 1 and 2, respectively, to 4.53 angstrom in 4 and there are related changes in the angles associated with the ligand set around the H-bridged osmium atoms. Introduction of the diphosphine ligands completely suppresses the ability to add CO, to insert acetylene to form a mu-eta(1), eta(2)-vinyl compound, and to exchange hydride ligands with styrene-d(8), which are reactions characteristic of [Os-3(mu-H)(2)(CO)(10)], Clusters 2 and 5-7 were also used to examine the potential of natural abundance Os-187 NMR spectroscopy through techniques based on inverse detection by HMQC, HSQC and HMBC spectroscopy. (c) 2005 Elsevier B.V. All rights reserved. (Less)
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https://lup.lub.lu.se/record/418204
- author
- Stchedroff, MJ ; Moberg, Viktor LU ; Rodriguez, Eduardo LU ; Aliev, AE ; Bottcher, J ; Steed, JW ; Nordlander, Ebbe LU ; Monari, M and Deeming, AJ
- organization
- publishing date
- 2006
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- NMR, chiral phosphine, osmium, cluster
- in
- Inorganica Chimica Acta
- volume
- 359
- issue
- 3
- pages
- 926 - 937
- publisher
- Elsevier
- external identifiers
-
- wos:000235109400026
- scopus:30944464417
- ISSN
- 0020-1693
- DOI
- 10.1016/j.ica.2005.06.048
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Inorganic chemistry (ceased) (LUR000010), Analytical Chemistry (S/LTH) (011001004), Chemical Physics (S) (011001060)
- id
- 6df098a4-c037-4cba-a89d-8e3475ddad7a (old id 418204)
- date added to LUP
- 2016-04-01 17:01:44
- date last changed
- 2022-01-28 23:50:14
@article{6df098a4-c037-4cba-a89d-8e3475ddad7a, abstract = {{Treatment of [Os-3(mu-H)(2)(CO)(10)] with the chiral diphosphines BINAP, tolBINAP [(R)-2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl], DIOP [(4R,5R)-(-)-O-isopropenylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino) butane] affords [Os-3(mu-H)(2)(CO)(8)(mu-L)] (L = BINAP (1), tolBINAP (2), DIOP (4)) in high yield. The X-ray structures for 1, 2 and 4 are reported, and structural and spectroscopic comparisons are made between these clusters and [Os-3(mu-H)(2)(CO)(8)(mu-L)] (L = dppm (5), dppe (6), dppp (7)) which were synthesised similarly. Compounds 5 to 7 were previously synthesised by hydrogenation of 1,2-[OS3(CO)(10)(mu-L)] but the route from [Os(mu-H)(2)(CO)(10)] is preferable. The H-bridged Os center dot center dot Os distances are similar in 1, 2 and 4 indicating that these species are formally unsaturated 46-electron clusters. The P center dot center dot center dot P distances vary from 4.24 to 4.30 angstrom in 1 and 2, respectively, to 4.53 angstrom in 4 and there are related changes in the angles associated with the ligand set around the H-bridged osmium atoms. Introduction of the diphosphine ligands completely suppresses the ability to add CO, to insert acetylene to form a mu-eta(1), eta(2)-vinyl compound, and to exchange hydride ligands with styrene-d(8), which are reactions characteristic of [Os-3(mu-H)(2)(CO)(10)], Clusters 2 and 5-7 were also used to examine the potential of natural abundance Os-187 NMR spectroscopy through techniques based on inverse detection by HMQC, HSQC and HMBC spectroscopy. (c) 2005 Elsevier B.V. All rights reserved.}}, author = {{Stchedroff, MJ and Moberg, Viktor and Rodriguez, Eduardo and Aliev, AE and Bottcher, J and Steed, JW and Nordlander, Ebbe and Monari, M and Deeming, AJ}}, issn = {{0020-1693}}, keywords = {{NMR; chiral phosphine; osmium; cluster}}, language = {{eng}}, number = {{3}}, pages = {{926--937}}, publisher = {{Elsevier}}, series = {{Inorganica Chimica Acta}}, title = {{Synthesis, characterisation and natural abundance Os-187 NMR spectroscopy of hydride bridged triosmium clusters with chiral diphosphine ligands}}, url = {{http://dx.doi.org/10.1016/j.ica.2005.06.048}}, doi = {{10.1016/j.ica.2005.06.048}}, volume = {{359}}, year = {{2006}}, }