Synthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide Anions
We have investigated the chemical reactivity of heptaatomic anionic clusters of the group 15 elements ([E7]3-/[HE 7]2-, E = P, As) toward the symmetric and asymmetrically substituted alkynes diphenylacetylene and phenylacetylene. The results reported herein, alongside a previous report on the reacti...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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2013
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| _version_ | 1797062529411710976 |
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| author | Turbervill, R Jupp, A McCullough, P Ergoecmen, D Goicoechea, J |
| author_facet | Turbervill, R Jupp, A McCullough, P Ergoecmen, D Goicoechea, J |
| author_sort | Turbervill, R |
| collection | OXFORD |
| description | We have investigated the chemical reactivity of heptaatomic anionic clusters of the group 15 elements ([E7]3-/[HE 7]2-, E = P, As) toward the symmetric and asymmetrically substituted alkynes diphenylacetylene and phenylacetylene. The results reported herein, alongside a previous report on the reactivity of such clusters toward acetylene, describe a versatile route by which to access otherwise elusive 1,2,3-tripnictolide anions of the general formula [E3C 2RR′]- (R = R′ = H, E = P (1), As (2); R = R′ = C6H5, E = P (3) As (4); R = H, R′ = C6H5, E = P (5), As (6)). These species can be isolated as [K(18-crown-6)]+ or [K(2,2,2-crypt)]+ salts. All anions were characterized by multielement NMR spectroscopy and electrospray mass spectrometry. In addition, single-crystal X-ray diffraction structures of the novel species [K(18-crown-6)(THF)2][3], [K(2,2,2-crypt)][4] ·xTHF (x = 0, 0.5), and [K(18-crown-6)THF][6] were also obtained. The chemical reactivity of these group 15 cyclopentadienyl analogues has been explored in a series of ligand displacement reactions with Mo(CO) 3(L)3 (L = CO, CH3CN) to yield the complex anions [(η5-E3C2H2)Mo(CO) 3]- (E = P (7), As (8)), [{η5-E 3C2(C6H5)2}Mo(CO) 3]- (E = P (9), As (10)), and [{η5-E 3C2H(C6H5)}Mo(CO)3] - (E = P (11), As (12)). © 2013 American Chemical Society. |
| first_indexed | 2024-03-06T20:46:49Z |
| format | Journal article |
| id | oxford-uuid:36303b3a-f768-4d3c-b9ed-a2b2f3d0d3f2 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T20:46:49Z |
| publishDate | 2013 |
| record_format | dspace |
| spelling | oxford-uuid:36303b3a-f768-4d3c-b9ed-a2b2f3d0d3f22022-03-26T13:36:20ZSynthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide AnionsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:36303b3a-f768-4d3c-b9ed-a2b2f3d0d3f2EnglishSymplectic Elements at Oxford2013Turbervill, RJupp, AMcCullough, PErgoecmen, DGoicoechea, JWe have investigated the chemical reactivity of heptaatomic anionic clusters of the group 15 elements ([E7]3-/[HE 7]2-, E = P, As) toward the symmetric and asymmetrically substituted alkynes diphenylacetylene and phenylacetylene. The results reported herein, alongside a previous report on the reactivity of such clusters toward acetylene, describe a versatile route by which to access otherwise elusive 1,2,3-tripnictolide anions of the general formula [E3C 2RR′]- (R = R′ = H, E = P (1), As (2); R = R′ = C6H5, E = P (3) As (4); R = H, R′ = C6H5, E = P (5), As (6)). These species can be isolated as [K(18-crown-6)]+ or [K(2,2,2-crypt)]+ salts. All anions were characterized by multielement NMR spectroscopy and electrospray mass spectrometry. In addition, single-crystal X-ray diffraction structures of the novel species [K(18-crown-6)(THF)2][3], [K(2,2,2-crypt)][4] ·xTHF (x = 0, 0.5), and [K(18-crown-6)THF][6] were also obtained. The chemical reactivity of these group 15 cyclopentadienyl analogues has been explored in a series of ligand displacement reactions with Mo(CO) 3(L)3 (L = CO, CH3CN) to yield the complex anions [(η5-E3C2H2)Mo(CO) 3]- (E = P (7), As (8)), [{η5-E 3C2(C6H5)2}Mo(CO) 3]- (E = P (9), As (10)), and [{η5-E 3C2H(C6H5)}Mo(CO)3] - (E = P (11), As (12)). © 2013 American Chemical Society. |
| spellingShingle | Turbervill, R Jupp, A McCullough, P Ergoecmen, D Goicoechea, J Synthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide Anions |
| title | Synthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide Anions |
| title_full | Synthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide Anions |
| title_fullStr | Synthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide Anions |
| title_full_unstemmed | Synthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide Anions |
| title_short | Synthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide Anions |
| title_sort | synthesis and characterization of free and coordinated 1 2 3 tripnictolide anions |
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