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A comparison of the ligating properties of the mixed P/O- and P/S-donor ligands Ph2P(CH2)(2)O(CH2)(2)O(CH2)(2)PPh2 and Ph2P(CH2)(2)S(CH2)(2)S(CH2)(2)PPh2 with Group 6 and 7 carbonyls

A comparison of the ligating properties of the mixed P/O- and P/S-donor ligands Ph2P(CH2)(2)O(CH2)(2)O(CH2)(2)PPh2 and Ph2P(CH2)(2)S(CH2)(2)S(CH2)(2)PPh2 with Group 6 and 7 carbonyls
A comparison of the ligating properties of the mixed P/O- and P/S-donor ligands Ph2P(CH2)(2)O(CH2)(2)O(CH2)(2)PPh2 and Ph2P(CH2)(2)S(CH2)(2)S(CH2)(2)PPh2 with Group 6 and 7 carbonyls
[M(CO)(4)(nbd)] (M = Cr or Mo) react with L-1 (Ph2P(CH2)(2)O(CH2)(2)O(CH2)(2)PPh2) to give the trans-[Cr(CO)(4)(L-1)] and cis-[Mo(CO)(4)(L-1)] respectively, both of which show coordination of L-1 through the P atoms only, giving 11-membered ring metallocyclic complexes. The crystal structure of [MO(CO)(4)(L-1)] confirms the cis-geometry of the product. The cis-[W(CO)(4)(L-1)] is obtained similarly from [W(CO)(4)(TMPA)]. Prolonged reaction of [MnCl(CO)(5)] with L-1 affords mer-trans-[MnCl(CO)(3)(L-1)], with L-1 functioning as a trans chelate via the phosphine functions. The kinetic product fac-[MnCl(CO)(3)(L-1)] is obtained when short reaction times are used. In contrast, [ReBr(CO)(5)] reacts with L-1 to give [ReBr(CO)(3)(L-1)] as a mixture of geometric isomers. Both 1:1 and 2:1 M:L-2 (L-2 = Ph2P(CH2)(2)S(CH2)(2)S(CH2)(2)PPh2) may be obtained for M = Mn(I) or Mn(0). The [MnCl(CO)(3)(L-2)] exists in solution as the fac isomer with L-2 functioning as a bidentate P,S-donor ligand giving a five-membered chelate ring and with the remaining thioether and phosphine functions uncoordinated. Addition of a further equivalent of [MnCl(CO)(5)] affords the binuclear fac-[{MnCl(CO)(3)}(mu(2)-L-2)], with symmetrical P,S-chelation to each metal centre. Similar behaviour is seen for Mo, thus cis-[{Mo(CO)(4)}(2)(mu(2)-L-2)] involves P,S-chelation to each Mo(0) ion. The related 1:1 species cis-[Mo(CO)(4)(L-2)] exists as a mixture of two compounds each with bidentate L-2 coordination, the P-2-chelate (11-membered ring metallocycle) and P,S-coordinated (five-membered chelate ring) species. The new compounds are characterised by microanalyses, IR, H-1-, C-13{H-1}-, P-31{H-1}-,Mn-55-NMR spectroscopy and mass spectrometry as appropriate. The different ligating properties of the related compounds L-1 and L-2 are discussed.
p/o- and p/s-donor ligands, nmr spectroscopy, x-ray crystallography, transition metal carbonyl complexes, ray crystal-structures, phosphathia complexes, redox properties, goldcomplexes, copper, silver, phosphine, halides, ethers
0022-328X
55-62
Heuer, Bjorn
88701b56-17d1-4284-953a-27f3ce13151f
Matthews, Melissa L.
48114504-dd8b-4879-b428-f31fada714e7
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Ripley, Mark
3b38c2c5-28d2-4a83-aa2c-8d744391be8b
Heuer, Bjorn
88701b56-17d1-4284-953a-27f3ce13151f
Matthews, Melissa L.
48114504-dd8b-4879-b428-f31fada714e7
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Ripley, Mark
3b38c2c5-28d2-4a83-aa2c-8d744391be8b

Heuer, Bjorn, Matthews, Melissa L., Reid, Gillian and Ripley, Mark (2002) A comparison of the ligating properties of the mixed P/O- and P/S-donor ligands Ph2P(CH2)(2)O(CH2)(2)O(CH2)(2)PPh2 and Ph2P(CH2)(2)S(CH2)(2)S(CH2)(2)PPh2 with Group 6 and 7 carbonyls. Journal of Organometallic Chemistry, 655 (1-2), 55-62. (doi:10.1016/S0022-328X(02)01413-4).

Record type: Article

Abstract

[M(CO)(4)(nbd)] (M = Cr or Mo) react with L-1 (Ph2P(CH2)(2)O(CH2)(2)O(CH2)(2)PPh2) to give the trans-[Cr(CO)(4)(L-1)] and cis-[Mo(CO)(4)(L-1)] respectively, both of which show coordination of L-1 through the P atoms only, giving 11-membered ring metallocyclic complexes. The crystal structure of [MO(CO)(4)(L-1)] confirms the cis-geometry of the product. The cis-[W(CO)(4)(L-1)] is obtained similarly from [W(CO)(4)(TMPA)]. Prolonged reaction of [MnCl(CO)(5)] with L-1 affords mer-trans-[MnCl(CO)(3)(L-1)], with L-1 functioning as a trans chelate via the phosphine functions. The kinetic product fac-[MnCl(CO)(3)(L-1)] is obtained when short reaction times are used. In contrast, [ReBr(CO)(5)] reacts with L-1 to give [ReBr(CO)(3)(L-1)] as a mixture of geometric isomers. Both 1:1 and 2:1 M:L-2 (L-2 = Ph2P(CH2)(2)S(CH2)(2)S(CH2)(2)PPh2) may be obtained for M = Mn(I) or Mn(0). The [MnCl(CO)(3)(L-2)] exists in solution as the fac isomer with L-2 functioning as a bidentate P,S-donor ligand giving a five-membered chelate ring and with the remaining thioether and phosphine functions uncoordinated. Addition of a further equivalent of [MnCl(CO)(5)] affords the binuclear fac-[{MnCl(CO)(3)}(mu(2)-L-2)], with symmetrical P,S-chelation to each metal centre. Similar behaviour is seen for Mo, thus cis-[{Mo(CO)(4)}(2)(mu(2)-L-2)] involves P,S-chelation to each Mo(0) ion. The related 1:1 species cis-[Mo(CO)(4)(L-2)] exists as a mixture of two compounds each with bidentate L-2 coordination, the P-2-chelate (11-membered ring metallocycle) and P,S-coordinated (five-membered chelate ring) species. The new compounds are characterised by microanalyses, IR, H-1-, C-13{H-1}-, P-31{H-1}-,Mn-55-NMR spectroscopy and mass spectrometry as appropriate. The different ligating properties of the related compounds L-1 and L-2 are discussed.

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Published date: 1 August 2002
Keywords: p/o- and p/s-donor ligands, nmr spectroscopy, x-ray crystallography, transition metal carbonyl complexes, ray crystal-structures, phosphathia complexes, redox properties, goldcomplexes, copper, silver, phosphine, halides, ethers

Identifiers

Local EPrints ID: 19772
URI: http://eprints.soton.ac.uk/id/eprint/19772
ISSN: 0022-328X
PURE UUID: 1d19c30b-e000-4615-9e82-81ef664a6227
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 20 Feb 2006
Last modified: 08 Jan 2022 02:38

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Contributors

Author: Bjorn Heuer
Author: Melissa L. Matthews
Author: Gillian Reid ORCID iD
Author: Mark Ripley

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