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Synthesis, characterisation and natural abundance Os-187 NMR spectroscopy of hydride bridged triosmium clusters with chiral diphosphine ligands

Stchedroff, MJ ; Moberg, Viktor LU ; Rodriguez, Eduardo LU ; Aliev, AE ; Bottcher, J ; Steed, JW ; Nordlander, Ebbe LU ; Monari, M and Deeming, AJ (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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publishing date
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
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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)
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6df098a4-c037-4cba-a89d-8e3475ddad7a (old id 418204)
date added to LUP
2016-04-01 17:01:44
date last changed
2020-10-11 04:45:04
@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},
  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},
}