Reactions of a Triazacyclononane-Supported Tantalum−Lithium Bridging Alkylidene with Organic Substrates

Schmidt, Joseph A. R.; Arnold, John

doi:10.1021/om020175c

Cited by 31 publications

(20 citation statements)

References 79 publications

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“…11 ppm, the downfield shift being characteristic of hydride ligands on a highly electrophilic metal center surrounded by hard donor groups [14] (cf. ½ðMe 3 SiCH 2 Þ 2 ðArN ¼ÞTaðl À HÞðl À g 1 : g 3 À Pr i 2 À tacnÞLi, 11.03 ppm [15]). These features are essentially invariant over the temperature range from À80 to 20°C.…”

Section: Reactions Of [( T Bu-l)mentioning

confidence: 99%

Complexes of tantalum with triaryloxides: Ligand and solvent effects on formation of hydride derivatives

Kawaguchi

Matsuo

2005

Journal of Organometallic Chemistry

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Section: Reactions Of [( T Bu-l)mentioning

confidence: 99%

Complexes of tantalum with triaryloxides: Ligand and solvent effects on formation of hydride derivatives

Kawaguchi

Matsuo

2005

Journal of Organometallic Chemistry

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“…20 Hz. Few one‐bond 7 Li– 1 H couplings can be found in the literature and those reported group in the 6–15 Hz interval [35,43–45] . Accordingly, the ca.…”

Section: Resultsmentioning

confidence: 81%

Supported σ‐Complexes of Li−C Bonds from Coordination of Monomeric Molecules of LiCH₃, LiCH₂CH₃ and LiC₆H₅ to Mo≣Mo Bonds

et al. 2022

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LiCH3 and LiCH2CH3 react with the complex [Mo2(H)2(μ‐AdDipp2)2(thf)2] (1⋅thf) with coordination of two molecules of LiCH2R (R=H, CH3) and formation of complexes [Mo2{μ‐HLi(thf)CH2R}2(AdDipp2)2], 5⋅LiCH3 and 5⋅LiCH2CH3, respectively (AdDipp2=HC(NDipp)2; Dipp=2,6‐iPr2C6H3; thf=C4H8O). Due to steric hindrance, only one molecule of LiC6H5 adds to 1⋅thf generating the complex [Mo2(H){μ‐HLi(thf)C6H5}(μ‐AdDipp2)2], (4⋅LiC6H5). Computational studies disclose the existence of five‐center six‐electron bonding within the H−Mo≣Mo−C−Li metallacycles, with a mostly covalent H−Mo≣Mo−C group and predominantly ionic Li−C and Li−H interactions. However, the latter bonds exhibit non‐negligible covalency, as indicated by X‐ray, computational data and the large one‐bond 6,7Li,1H and 6,7Li,13C NMR coupling constants found for the three‐atom H−Li−C chains. By contrast, the phenyl group in 4⋅LiC6H5 coordinates in an η2 fashion to the lithium atom through the ipso and one of the ortho carbon atoms.

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“…Few one-bond 7 Li-1 H couplings can be found in the literature and those reported group in the 6-15 Hz interval. [35,[43][44][45] Accordingly, the ca. 20 Hz values found in this work are the largest thus far measured and can be taken as indicative of a significant degree of covalency in the MoÀ HÀ Li bridging bonds.…”

Section: Resultsmentioning

confidence: 99%

Supported σ‐Complexes of Li−C Bonds from Coordination of Monomeric Molecules of LiCH₃, LiCH₂CH₃ and LiC₆H₅ to Mo≣Mo Bonds

et al. 2022

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LiCH 3 and LiCH 2 CH 3 react with the complex [Mo 2 (H) 2 (μ-Ad Dipp2 ) 2 (thf) 2 ] (1•thf) with coordination of two molecules of LiCH 2 R (R=H, CH 3 ) and formation of complexes [Mo 2 {μ-HLi(thf)CH 2 R} 2 (Ad Dipp2 ) 2 ], 5•LiCH 3 and 5•LiCH 2 CH 3 , respectively (Ad Dipp2 = HC(NDipp) 2 ; Dipp = 2,6-i Pr 2 C 6 H 3 ; thf = C 4 H 8 O). Due to steric hindrance, only one molecule of LiC 6 H 5 adds to 1•thf generating the complex [Mo 2 (H){μ-HLi-(thf)C 6 H 5 }(μ-Ad Dipp2 ) 2 ], (4•LiC 6 H 5). Computational studies disclose the existence of five-center six-electron bonding within the HÀ Mo� � MoÀ CÀ Li metallacycles, with a mostly covalent HÀ Mo� � MoÀ C group and predominantly ionic LiÀ C and LiÀ H interactions. However, the latter bonds exhibit non-negligible covalency, as indicated by X-ray, computational data and the large one-bond 6,7 Li, 1 H and 6,7 Li, 13 C NMR coupling constants found for the three-atom HÀ LiÀ C chains. By contrast, the phenyl group in 4•LiC 6 H 5 coordinates in an η 2 fashion to the lithium atom through the ipso and one of the ortho carbon atoms.

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Reactions of a Triazacyclononane-Supported Tantalum−Lithium Bridging Alkylidene with Organic Substrates

Cited by 31 publications

References 79 publications

Complexes of tantalum with triaryloxides: Ligand and solvent effects on formation of hydride derivatives

Complexes of tantalum with triaryloxides: Ligand and solvent effects on formation of hydride derivatives

Supported σ‐Complexes of Li−C Bonds from Coordination of Monomeric Molecules of LiCH₃, LiCH₂CH₃ and LiC₆H₅ to Mo≣Mo Bonds

Supported σ‐Complexes of Li−C Bonds from Coordination of Monomeric Molecules of LiCH₃, LiCH₂CH₃ and LiC₆H₅ to Mo≣Mo Bonds

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Reactions of a Triazacyclononane-Supported Tantalum−Lithium Bridging Alkylidene with Organic Substrates

Cited by 31 publications

References 79 publications

Complexes of tantalum with triaryloxides: Ligand and solvent effects on formation of hydride derivatives

Complexes of tantalum with triaryloxides: Ligand and solvent effects on formation of hydride derivatives

Supported σ‐Complexes of Li−C Bonds from Coordination of Monomeric Molecules of LiCH3, LiCH2CH3 and LiC6H5 to Mo≣Mo Bonds

Supported σ‐Complexes of Li−C Bonds from Coordination of Monomeric Molecules of LiCH3, LiCH2CH3 and LiC6H5 to Mo≣Mo Bonds

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Product

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Supported σ‐Complexes of Li−C Bonds from Coordination of Monomeric Molecules of LiCH₃, LiCH₂CH₃ and LiC₆H₅ to Mo≣Mo Bonds

Supported σ‐Complexes of Li−C Bonds from Coordination of Monomeric Molecules of LiCH₃, LiCH₂CH₃ and LiC₆H₅ to Mo≣Mo Bonds