Silyl Hydrides of Tantalum Supported by Cyclopentadienyl-imido Ligand Sets: Syntheses, X-ray, NMR, and DFT Studies

Reactions of the imido complex Cp(ArN)Ta(PMe3)2 (1, Ar = 2,6-diisopropylphenyl) with silanes afford the silyl hydrides Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) (2b−e) and Cp(ArN)Ta(PMe3)(H)(SiPhMeH) (2a) as the first kinetic products. However, the hydride compounds Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) are metas...

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Veröffentlicht in:Organometallics 2008-11, Vol.27 (22), p.5968-5977
Hauptverfasser: Ignatov, Stanislav K, Rees, Nicholas H, Merkoulov, Alexei A, Dubberley, Stuart R, Razuvaev, Alexei G, Mountford, Philip, Nikonov, Georgii I
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container_title Organometallics
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creator Ignatov, Stanislav K
Rees, Nicholas H
Merkoulov, Alexei A
Dubberley, Stuart R
Razuvaev, Alexei G
Mountford, Philip
Nikonov, Georgii I
description Reactions of the imido complex Cp(ArN)Ta(PMe3)2 (1, Ar = 2,6-diisopropylphenyl) with silanes afford the silyl hydrides Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) (2b−e) and Cp(ArN)Ta(PMe3)(H)(SiPhMeH) (2a) as the first kinetic products. However, the hydride compounds Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) are metastable and, first, rearrange in the presence of phosphine to the chlorides Cp(ArN)Ta(PMe3)(Cl)(SiHR n Cl2−n ) (5) and then decompose to Cp(ArN)Ta(PMe3)(Cl)(H) (4) and eventually to Cp(ArN)Ta(PMe3)Cl2 (3). Complexes with a smaller Ar′ substituent at nitrogen (Ar′ = 2,6-dimethylphenyl) react faster, as do more Lewis acidic silanes. The occurrence of interligand hypervalent interactions in the tantalum complexes Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) has been revealed by X-ray structure analysis, DFT calculations, and the experimental determination of the sign of the coupling constant J(Si−H). The J(Si−H) was found to be negative for Cp(ArN)Ta(PMe3)(H)(SiMe n Cl3−n ) (J(Si−H) = −40 Hz for n = 1; J(Si−H) = −50 Hz for n = 0), indicative of the presence of Si−H bonding, but positive for Cp(ArN)Ta(PMe3)(H)(SiMeHPh) (J(Si−H) = +14 Hz), suggesting the absence of direct Si−H interactions. A DFT study of the mechanism of silane coupling with the model imido complex Cp(MeN)Ta(PMe3)2 established the feasibility of the direct addition of silanes HSiMe n Cl3−n (n = 1−3) to the imido group to give the adduct Cp(MeN{→SiR3-H})Ta(PMe3)2, as previously found in the related niobium chemistry.
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However, the hydride compounds Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) are metastable and, first, rearrange in the presence of phosphine to the chlorides Cp(ArN)Ta(PMe3)(Cl)(SiHR n Cl2−n ) (5) and then decompose to Cp(ArN)Ta(PMe3)(Cl)(H) (4) and eventually to Cp(ArN)Ta(PMe3)Cl2 (3). Complexes with a smaller Ar′ substituent at nitrogen (Ar′ = 2,6-dimethylphenyl) react faster, as do more Lewis acidic silanes. The occurrence of interligand hypervalent interactions in the tantalum complexes Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) has been revealed by X-ray structure analysis, DFT calculations, and the experimental determination of the sign of the coupling constant J(Si−H). The J(Si−H) was found to be negative for Cp(ArN)Ta(PMe3)(H)(SiMe n Cl3−n ) (J(Si−H) = −40 Hz for n = 1; J(Si−H) = −50 Hz for n = 0), indicative of the presence of Si−H bonding, but positive for Cp(ArN)Ta(PMe3)(H)(SiMeHPh) (J(Si−H) = +14 Hz), suggesting the absence of direct Si−H interactions. A DFT study of the mechanism of silane coupling with the model imido complex Cp(MeN)Ta(PMe3)2 established the feasibility of the direct addition of silanes HSiMe n Cl3−n (n = 1−3) to the imido group to give the adduct Cp(MeN{→SiR3-H})Ta(PMe3)2, as previously found in the related niobium chemistry.</description><identifier>ISSN: 0276-7333</identifier><identifier>EISSN: 1520-6041</identifier><identifier>DOI: 10.1021/om800553y</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Organometallics, 2008-11, Vol.27 (22), p.5968-5977</ispartof><rights>Copyright © 2008 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a297t-a0955c30c3a7ee88ab148cdaba3f070ac97cc1fbda31a9a2672295abc25577533</citedby><cites>FETCH-LOGICAL-a297t-a0955c30c3a7ee88ab148cdaba3f070ac97cc1fbda31a9a2672295abc25577533</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/om800553y$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/om800553y$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids></links><search><creatorcontrib>Ignatov, Stanislav K</creatorcontrib><creatorcontrib>Rees, Nicholas H</creatorcontrib><creatorcontrib>Merkoulov, Alexei A</creatorcontrib><creatorcontrib>Dubberley, Stuart R</creatorcontrib><creatorcontrib>Razuvaev, Alexei G</creatorcontrib><creatorcontrib>Mountford, Philip</creatorcontrib><creatorcontrib>Nikonov, Georgii I</creatorcontrib><title>Silyl Hydrides of Tantalum Supported by Cyclopentadienyl-imido Ligand Sets: Syntheses, X-ray, NMR, and DFT Studies</title><title>Organometallics</title><addtitle>Organometallics</addtitle><description>Reactions of the imido complex Cp(ArN)Ta(PMe3)2 (1, Ar = 2,6-diisopropylphenyl) with silanes afford the silyl hydrides Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) (2b−e) and Cp(ArN)Ta(PMe3)(H)(SiPhMeH) (2a) as the first kinetic products. However, the hydride compounds Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) are metastable and, first, rearrange in the presence of phosphine to the chlorides Cp(ArN)Ta(PMe3)(Cl)(SiHR n Cl2−n ) (5) and then decompose to Cp(ArN)Ta(PMe3)(Cl)(H) (4) and eventually to Cp(ArN)Ta(PMe3)Cl2 (3). Complexes with a smaller Ar′ substituent at nitrogen (Ar′ = 2,6-dimethylphenyl) react faster, as do more Lewis acidic silanes. The occurrence of interligand hypervalent interactions in the tantalum complexes Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) has been revealed by X-ray structure analysis, DFT calculations, and the experimental determination of the sign of the coupling constant J(Si−H). The J(Si−H) was found to be negative for Cp(ArN)Ta(PMe3)(H)(SiMe n Cl3−n ) (J(Si−H) = −40 Hz for n = 1; J(Si−H) = −50 Hz for n = 0), indicative of the presence of Si−H bonding, but positive for Cp(ArN)Ta(PMe3)(H)(SiMeHPh) (J(Si−H) = +14 Hz), suggesting the absence of direct Si−H interactions. 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However, the hydride compounds Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) are metastable and, first, rearrange in the presence of phosphine to the chlorides Cp(ArN)Ta(PMe3)(Cl)(SiHR n Cl2−n ) (5) and then decompose to Cp(ArN)Ta(PMe3)(Cl)(H) (4) and eventually to Cp(ArN)Ta(PMe3)Cl2 (3). Complexes with a smaller Ar′ substituent at nitrogen (Ar′ = 2,6-dimethylphenyl) react faster, as do more Lewis acidic silanes. The occurrence of interligand hypervalent interactions in the tantalum complexes Cp(ArN)Ta(PMe3)(H)(SiR n Cl3−n ) has been revealed by X-ray structure analysis, DFT calculations, and the experimental determination of the sign of the coupling constant J(Si−H). The J(Si−H) was found to be negative for Cp(ArN)Ta(PMe3)(H)(SiMe n Cl3−n ) (J(Si−H) = −40 Hz for n = 1; J(Si−H) = −50 Hz for n = 0), indicative of the presence of Si−H bonding, but positive for Cp(ArN)Ta(PMe3)(H)(SiMeHPh) (J(Si−H) = +14 Hz), suggesting the absence of direct Si−H interactions. A DFT study of the mechanism of silane coupling with the model imido complex Cp(MeN)Ta(PMe3)2 established the feasibility of the direct addition of silanes HSiMe n Cl3−n (n = 1−3) to the imido group to give the adduct Cp(MeN{→SiR3-H})Ta(PMe3)2, as previously found in the related niobium chemistry.</abstract><pub>American Chemical Society</pub><doi>10.1021/om800553y</doi><tpages>10</tpages></addata></record>
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