A monomeric methyllithium complex: synthesis and structure

Davison, Nathan; Falbo, Emanuele; Waddell, Paul G.; Penfold, Thomas J.; Lu, Erli

doi:10.1039/d1cc01420j

Cited by 16 publications

(49 citation statements)

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“…Following regular work‐up, a yellow crystalline solid was isolated and identified as complex 5⋅LiCH 3 , incorporating two molecules of LiCH 3 to the coordination sphere of the Mo≣Mo bond (Scheme 1 a). Partial decomposition occurred [33] as denoted by the formation of small quantities of LiAd Dipp2 . 1 H and 7 Li NMR monitoring of the transformation utilizing 1 : 1 and 1 : 2 molar mixtures of reagents, revealed initial formation of a reactive intermediate 4⋅LiCH 3 , that could not be isolated as a pure solid but was fully characterized by solution multinuclear NMR experiments and computationally confirmed as a minimum energy structure.…”

Section: Resultsmentioning

confidence: 99%

“…[ 28 , 29 , 30 , 31 ] Although LiC 6 H 5 exists as a monomer in [Li(C 6 H 5 )(pmdta)] [32] (pmdta=pentamethyldiethylenetriamine, NMe(CH 2 CH 2 NMe 2 ) 2 ), we are not aware of the existence of related monomeric complexes of LiCH 3 and LiCH 2 CH 3 . [33] We have also studied the reaction of the dimethyl complex 2⋅thf [26] with LiAlH 4 as a source of LiH. Contradicting our expectations, instead of forming the anticipated Mo−C−Li−H−Mo metallacyclic rings, LiH promoted Mo−CH 3 to Mo−H bond metathesis [34] and elimination of LiCH 3 , ultimately generating a hydride‐rich Mo 6 Li 9 H 18 cluster, recently prepared by our group by a different procedure.…”

Section: Introductionmentioning

confidence: 90%

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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

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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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 90%

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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“…A comparison between the structures of complex 2 and our previous reported [Li(CH 3 )(κ 3 - N , N ′, N ′′-DETAN)] ( 3 ) is intriguing (see Chart 2 ). 34 The DETAN ligand in 2 adopts a κ 4 - N , N ′, N ″, N ′′′ mode, while in 3 it is in a κ 3 - N , N ′, N ′′mode. The key difference between 2 and 3 is that one out of the three side arms of the DETAN coordinates in 2 , while none of them coordinates in 3 .…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“… a Data taken from ref ( 34 ). The DETAN ligand is in κ 4 - N , N ′, N ″, N ′′′ ( 2 ) and κ 3 - N , N ′, N ′′ ( 3 ) mode, respectively.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

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Versatile Coordination Modes of Multidentate Neutral Amine Ligands with Group 1 Metal Cations

et al. 2022

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This work comprehensively investigated the coordination chemistry of a hexa -dentate neutral amine ligand, namely, N,N′,N” - tris -(2- N -diethylaminoethyl)-1,4,7-triaza-cyclononane (DETAN), with group-1 metal cations (Li + , Na + , K + , Rb + , Cs + ). Versatile coordination modes were observed, from four-coordinate trigonal pyramidal to six-coordinate trigonal prismatic, depending on the metal ionic radii and metal’s substituent. For comparison, the coordination chemistry of a tetra -dentate tris -[2-(dimethylamino)ethyl]amine (Me 6 Tren) ligand was also studied. This work defines the available coordination modes of two multidentate amine ligands (DETAN and Me 6 Tren), guiding future applications of these ligands for pursuing highly reactive and elusive s-block and rare-earth metal complexes.

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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

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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A monomeric methyllithium complex: synthesis and structure

Abstract: Methyllithium (MeLi) is the parent archetypical organolithium complex and its monomeric form is vital for understanding the ubiquitous organolithium-mediated reactions. However, despite being pursued for decades, to the best of...

Cited by 16 publications

References 52 publications

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

Versatile Coordination Modes of Multidentate Neutral Amine Ligands with Group 1 Metal Cations

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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A monomeric methyllithium complex: synthesis and structure

Abstract: Methyllithium (MeLi) is the parent archetypical organolithium complex and its monomeric form is vital for understanding the ubiquitous organolithium-mediated reactions. However, despite being pursued for decades, to the best of...

Cited by 16 publications

References 52 publications

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

Versatile Coordination Modes of Multidentate Neutral Amine Ligands with Group 1 Metal Cations

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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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

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