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Hybrid dibismuthines and distibines: preparation and properties of antimony and bismuth oxygen, sulfur, and nitrogen donor ligands

Hybrid dibismuthines and distibines: preparation and properties of antimony and bismuth oxygen, sulfur, and nitrogen donor ligands
Hybrid dibismuthines and distibines: preparation and properties of antimony and bismuth oxygen, sulfur, and nitrogen donor ligands
The hybrid dibismuthines O{(CH2)2BiPh2}2, MeN(CH2-2-C6H4BiR2)2, and S(CH2-2-C6H4BiR2)2 (R = Me, Ph), have been prepared and characterized by microanalysis, 1H and 13C{1H} NMR spectroscopy, and FAB mass spectrometry. The X-ray structures of O{(CH2)2BiPh2}2 and S(CH2-2-C6H4BiPh2)2 show close to symmetrical hypervalent interactions between the O or S atoms and both bismuth centers. The antimony analogue S(CH2-2-C6H4SbMe2)2 is quaternized by MeI to [S(CH2-2-C6H4SbMe3)2]I2, which also shows a hypervalent S···Sb interaction, but in this case to only a single antimony center. Complexes of these and related ligands with the CpFe(CO)2+ group, of the type [{CpFe(CO)2}2L][BF4]2 (L = O{(CH2)2BiPh2}2, MeN(CH2-2-C6H4BiR2)2, S(CH2-2-C6H4BiR2)2, O{(CH2)2SbR2}2, S(CH2-2-C6H4SbMe2)2, MeN(CH2-2-C6H4SbMe2)2, Ph2Sb(CH2)3SbPh2), have been prepared and characterized by microanalysis (antimony complexes only), 1H and 13C{1H} NMR and IR spectroscopy, and ES+ mass spectrometry. The X-ray crystal structure of [{CpFe(CO)2}2{O{(CH2)2SbMe2}2}][BF4]2 shows a hypervalent Sb···O contact to one of the antimony centers, whereas no hypervalent contacts are seen in the structure of [{CpFe(CO)2}2{MeN(CH2-2-C6H4SbMe2)2}][BF4]2. IR (carbonyl region) and NMR spectroscopy indicate that, uniquely, [{CpFe(CO)2}2{MeN(CH2-2-C6H4BiPh2)2}][BF4]2 shows hypervalent N···Bi interactions in both the solid and solution, but for the other dibismuthine complexes, there is evidence for inequivalence of the iron centers (and hence hypervalency) only in the solid state. Spectroscopic data indicate that hypervalent interactions are absent in [{CpFe(CO)2}2{MeN(CH2-2-C6H4SbMe2)2}][BF4]2 and [{CpFe(CO)2}2{S(CH2-2-C6H4SbMe2)2}][BF4]2, but present in solid [{CpFe(CO)2}2{O{(CH2)2SbR2}2}][BF4]2. The preparation and X-ray structure of [CpFe(CO)2{BiPh2(o-C6H4OMe)}][BF4] is also reported, but attempts to isolate [CpFe(CO)2(BiPhMe2)]][BF4] resulted in rapid scrambling of the substituents at bismuth to give [CpFe(CO)2(BiPh3?nMen)][BF4] (n = 0?3).
0276-7333
895-904
Benjamin, Sophie L.
33433a1a-691e-439e-a277-e7577bde3a1a
Karagiannidis, Louise
fd53b5b4-0fc2-41ff-a665-e3185e8c8589
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Rogers, Michael
aeb20884-4097-4288-9365-7afd6780cd05
Benjamin, Sophie L.
33433a1a-691e-439e-a277-e7577bde3a1a
Karagiannidis, Louise
fd53b5b4-0fc2-41ff-a665-e3185e8c8589
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Rogers, Michael
aeb20884-4097-4288-9365-7afd6780cd05

Benjamin, Sophie L., Karagiannidis, Louise, Levason, William, Reid, Gillian and Rogers, Michael (2011) Hybrid dibismuthines and distibines: preparation and properties of antimony and bismuth oxygen, sulfur, and nitrogen donor ligands. Organometallics, 30 (4), 895-904. (doi:10.1021/om1010148).

Record type: Article

Abstract

The hybrid dibismuthines O{(CH2)2BiPh2}2, MeN(CH2-2-C6H4BiR2)2, and S(CH2-2-C6H4BiR2)2 (R = Me, Ph), have been prepared and characterized by microanalysis, 1H and 13C{1H} NMR spectroscopy, and FAB mass spectrometry. The X-ray structures of O{(CH2)2BiPh2}2 and S(CH2-2-C6H4BiPh2)2 show close to symmetrical hypervalent interactions between the O or S atoms and both bismuth centers. The antimony analogue S(CH2-2-C6H4SbMe2)2 is quaternized by MeI to [S(CH2-2-C6H4SbMe3)2]I2, which also shows a hypervalent S···Sb interaction, but in this case to only a single antimony center. Complexes of these and related ligands with the CpFe(CO)2+ group, of the type [{CpFe(CO)2}2L][BF4]2 (L = O{(CH2)2BiPh2}2, MeN(CH2-2-C6H4BiR2)2, S(CH2-2-C6H4BiR2)2, O{(CH2)2SbR2}2, S(CH2-2-C6H4SbMe2)2, MeN(CH2-2-C6H4SbMe2)2, Ph2Sb(CH2)3SbPh2), have been prepared and characterized by microanalysis (antimony complexes only), 1H and 13C{1H} NMR and IR spectroscopy, and ES+ mass spectrometry. The X-ray crystal structure of [{CpFe(CO)2}2{O{(CH2)2SbMe2}2}][BF4]2 shows a hypervalent Sb···O contact to one of the antimony centers, whereas no hypervalent contacts are seen in the structure of [{CpFe(CO)2}2{MeN(CH2-2-C6H4SbMe2)2}][BF4]2. IR (carbonyl region) and NMR spectroscopy indicate that, uniquely, [{CpFe(CO)2}2{MeN(CH2-2-C6H4BiPh2)2}][BF4]2 shows hypervalent N···Bi interactions in both the solid and solution, but for the other dibismuthine complexes, there is evidence for inequivalence of the iron centers (and hence hypervalency) only in the solid state. Spectroscopic data indicate that hypervalent interactions are absent in [{CpFe(CO)2}2{MeN(CH2-2-C6H4SbMe2)2}][BF4]2 and [{CpFe(CO)2}2{S(CH2-2-C6H4SbMe2)2}][BF4]2, but present in solid [{CpFe(CO)2}2{O{(CH2)2SbR2}2}][BF4]2. The preparation and X-ray structure of [CpFe(CO)2{BiPh2(o-C6H4OMe)}][BF4] is also reported, but attempts to isolate [CpFe(CO)2(BiPhMe2)]][BF4] resulted in rapid scrambling of the substituents at bismuth to give [CpFe(CO)2(BiPh3?nMen)][BF4] (n = 0?3).

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e-pub ahead of print date: 24 January 2011
Published date: 28 February 2011
Organisations: Chemistry

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Local EPrints ID: 178893
URI: https://eprints.soton.ac.uk/id/eprint/178893
ISSN: 0276-7333
PURE UUID: 66dc1cd9-d5fc-4829-8961-c17825b9c8e3
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 31 Mar 2011 12:51
Last modified: 19 Nov 2019 02:04

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