Synthesis and properties of a new nine-membered triphospha-macrocyclic complex via a manganese(I) tricarbonyl template
Synthesis and properties of a new nine-membered triphospha-macrocyclic complex via a manganese(I) tricarbonyl template
Reaction of the primary diphosphine H2P(CH2)2PH2 with [MnBr(CO)5], followed by removal of the bromide by treatment with AgOTf (OTf = CF3SO3) and addition of PAr3 (Ar = o-C6H4F), gives the acyclic precursor complex, fac-[Mn(CO)3{H2P(CH2)2PH2}(PAr3)][OTf], thus positioning the primary phosphine functions adjacent to the o-fluorophenyl substituents. The identity of this species was confirmed by multinuclear NMR (1H, 19F{1H}, 31P{1H} and 55Mn) and IR spectroscopic analysis, as well as from a single crystal X-ray analysis. Subsequent treatment of this complex with KOtBu (potassium tertiary butoxide) causes a double P-C coupling reaction, with defluorination of two aryl groups, and leads to formation of a nine-membered triphosphine macrocyclic complex. Methylation (KOtBu/MeI) of the two remaining secondary phosphine function yields the complex [Mn(CO)3(1)][OTf], which has been characterised similarly by multinuclear NMR and IR spectroscopy, and by electrospray mass spectrometry. A single crystal X-ray structure determination confirms the distorted octahedral coordination at Mn(I), with the triphosphine macrocycle occupying three mutually facial coordination sites. As expected, this complex is extremely thermodynamically stable and kinetically inert, being unaffected by prolonged refluxing with either Me3NO or thiophenolate in MeCN.
Macrocycle, Manganese, Phosphine, Triphosphacyclononane, X-Ray structure
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
15 September 2022
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian, Levason, William and Reid, Gillian
(2022)
Synthesis and properties of a new nine-membered triphospha-macrocyclic complex via a manganese(I) tricarbonyl template.
Journal of Molecular Structure, 1264, [133268].
(doi:10.1016/j.molstruc.2022.133268).
Abstract
Reaction of the primary diphosphine H2P(CH2)2PH2 with [MnBr(CO)5], followed by removal of the bromide by treatment with AgOTf (OTf = CF3SO3) and addition of PAr3 (Ar = o-C6H4F), gives the acyclic precursor complex, fac-[Mn(CO)3{H2P(CH2)2PH2}(PAr3)][OTf], thus positioning the primary phosphine functions adjacent to the o-fluorophenyl substituents. The identity of this species was confirmed by multinuclear NMR (1H, 19F{1H}, 31P{1H} and 55Mn) and IR spectroscopic analysis, as well as from a single crystal X-ray analysis. Subsequent treatment of this complex with KOtBu (potassium tertiary butoxide) causes a double P-C coupling reaction, with defluorination of two aryl groups, and leads to formation of a nine-membered triphosphine macrocyclic complex. Methylation (KOtBu/MeI) of the two remaining secondary phosphine function yields the complex [Mn(CO)3(1)][OTf], which has been characterised similarly by multinuclear NMR and IR spectroscopy, and by electrospray mass spectrometry. A single crystal X-ray structure determination confirms the distorted octahedral coordination at Mn(I), with the triphosphine macrocycle occupying three mutually facial coordination sites. As expected, this complex is extremely thermodynamically stable and kinetically inert, being unaffected by prolonged refluxing with either Me3NO or thiophenolate in MeCN.
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P3 manuscript final revised 04_05_22 clean + full refs
- Accepted Manuscript
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1-s2.0-S0022286022009243-main (1)
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Accepted/In Press date: 8 May 2022
e-pub ahead of print date: 10 May 2022
Published date: 15 September 2022
Additional Information:
Funding Information:
We thank the EPSRC for funding through the ADEPT project (EP/N035437/1).
Publisher Copyright:
© 2022
Keywords:
Macrocycle, Manganese, Phosphine, Triphosphacyclononane, X-Ray structure
Identifiers
Local EPrints ID: 467958
URI: http://eprints.soton.ac.uk/id/eprint/467958
ISSN: 0022-2860
PURE UUID: 502b0c4c-142d-4e45-8d1a-0a6c5d4b43c5
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Date deposited: 26 Jul 2022 17:05
Last modified: 18 Mar 2024 02:39
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