Solid-state and solution studies of lithiated 2-carbomethoxycyclohexanone dimethylhydrazone and lithiated cyclohexanone phenylimine

Wanat, Robert A.; Collum, David B.; Duyne, G. Van; Clardy, Jon; DePue, Randall T.

doi:10.1021/ja00272a042

Cited by 77 publications

(30 citation statements)

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“…The average Li-N distances are 2.034(4) Å for Li1 and 2.053(4) Å for Li2 (Table 2). They are comparable to those distances found in some symmetric dimeric lithium amides such as [Li{HN(iPr) 2 }N-1-c-C 6 H 9 Ph] 2 (Li-N = 2.05 Å), [24] [Li(THF)HMCTS] 2 (Li-N = 2.04 Å), [25] [Li(THF)NSiMe 3 HMCTS] 2 (Li-N = 2.04 Å) [26] [21] which is presumably due to the higher coordination number of the Li ion and the bridging mode …”

Section: Structure Ofsupporting

confidence: 80%

μ‐Coordination Chemistry of NO Ligands: Adducts of trans‐Mo(dmpe)₂(Cl)(NO) with Lithium Salts

2006

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Reaction of trans-Mo(dmpe) 2 (Cl)(NO) (1) [dmpe = bis(dimethylphosphanyl)ethane] with lithium triethylborohydride and lithium bis(trimethylsilyl)amide affords the adducts [Mo(dmpe) 2 (Cl)(NO)(LiHBEt 3 )] n (2) and {Mo(dmpe) 2 (Cl)-(NO)[LiN(SiMe 3 ) 2 ] 2 } n (3), respectively, and the reaction of 1 with n-butyllithium and iodomethane generates the complex [Mo(dmpe) 2 (Cl)(NO)] 3 (LiI) 2 (4). Complexes 2-4 have been characterized by elemental analysis, IR spectroscopy, NMR spectroscopy, and single-crystal X-ray diffraction analysis. The structure of 2 shows an infinite one-dimensional "zigzag" chain constructed from an alternating arrangement of Mo(dmpe) 2 (Cl)(NO) and LiHBEt 3 moieties, whereas the Transition metal nitrosyl complexes have received considerable attention for many years due to their potential applications as catalysts in organic synthesis and small molecule activation. [1,2] Our interest in this field lies mainly in the chemistry of nitrosyl hydrido transition metal complexes. In this context a series of compounds of manganese, [3] rhenium, [4] chromium, [5] tungsten, [6] and molybdenum [7] have been synthesized and explored in particular with regard to hydride-transfer chemistry. It has been found that the nitrosyl group exhibits versatile functions in such compounds. It can stabilize the different oxidation states of the metal center, [1,8] and it can induce quite strong hydridic polarization by the "nitrosyl effect"; thus the nitrosyl group promotes the activation of the metal-hydrogen bond.[9] Additionally, the nitrosyl group can show a certain amount of Lewis base behavior by interacting with Lewis acids at the oxygen atom site. [8,10] The nitrosyl ligand/Lewis acid interactions have been found to sometimes play a key role in organic (organometallic) syntheses and reactions. For example, the catalytic oxidation of alcohols by a cobalt nitro/nitrosyl couple with the use of molecular oxygen as an oxidant was found to be facilitated by Lewis acids such as BF 3 ·Et 2 O or LiPF 6 . [11] The effects of the Lewis acids in the reaction were attributed to their interactions with nitro and nitrosyl ligands. In dinitrosyl complexes Re(H)(NO) 2 (PR 3 ) 2 (R = iPr, Cy), one

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Section: Structure Ofsupporting

confidence: 80%

μ‐Coordination Chemistry of NO Ligands: Adducts of trans‐Mo(dmpe)₂(Cl)(NO) with Lithium Salts

2006

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“…Imine 22 was chosen for these experiments because the corresponding lithium salt 22-Li could be isolated in pure form following aknown procedure. [17] After ar eactiont ime of 20 h, we observed completec onversion to the corresponding amine (Scheme6,r eaction 1), as in the reactionofthe parent imine with LiN(SiMe 3 ) 2 (Scheme 6, reaction 3). In addition, the analogousr eactions of metalloenamine 22-Li (Scheme 6, reaction 2) and imine 22 with LiN-(SiMe 3 ) 2 (Scheme6,r eaction4)w ere conducted under 100 bar of D 2 .B oth reactions gave very little conversion to product, which is consistentwith astrong kinetic isotope effect.…”

supporting

confidence: 80%

“…To examine whether an α‐deprotonated imine is sufficiently basic to induce H 2 splitting, a suspension of the lithiated imine 22‐Li , free from HN(SiMe 3 ) 2 and LiN(SiMe 3 ) 2 , was treated with H 2 (100 bar, 80 °C in toluene). Imine 22 was chosen for these experiments because the corresponding lithium salt 22‐Li could be isolated in pure form following a known procedure . After a reaction time of 20 h, we observed complete conversion to the corresponding amine (Scheme , reaction 1), as in the reaction of the parent imine with LiN(SiMe 3 ) 2 (Scheme , reaction 3).…”

Section: Methodsmentioning

confidence: 99%

H₂ Activation by Non‐Transition‐Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe₃)₂

Elliott

Martí

Mauleón

et al. 2019

Chemistry A European J

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In recent years, H2 activation at non‐transition‐metal centers has met with increasing attention. Here, a system in which H2 is activated and transferred to aldimines and ketimines using substoichiometric amounts of lithium bis(trimethylsilyl)amide is reported. Notably, the reaction tolerates the presence of acidic protons in the α‐position. Mechanistic investigations indicated that the reaction proceeds via a lithium hydride intermediate as the actual reductant.

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“…Further studies showed how the substituent(s) on the cyclohexanone imine could influence the stereochemistry, the axial position still remaining more favored. 148,149 X-ray and theoretical studies on hydrazone lithioanions were done to try to explain the often >98% axial selectivity. Earlier hypotheses reported chelation 147,156 and orbital symmetry to explain the strong preference for the substituent on the imine nitrogen atom to orient Z to the carbanionic carbon.…”

Section: Structural Datamentioning

confidence: 99%

1-Azaallylic Anions in Heterocyclic Chemistry

2004

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Solid-state and solution studies of lithiated 2-carbomethoxycyclohexanone dimethylhydrazone and lithiated cyclohexanone phenylimine

Cited by 77 publications

References 0 publications

μ‐Coordination Chemistry of NO Ligands: Adducts of trans‐Mo(dmpe)₂(Cl)(NO) with Lithium Salts

μ‐Coordination Chemistry of NO Ligands: Adducts of trans‐Mo(dmpe)₂(Cl)(NO) with Lithium Salts

H₂ Activation by Non‐Transition‐Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe₃)₂

1-Azaallylic Anions in Heterocyclic Chemistry

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Solid-state and solution studies of lithiated 2-carbomethoxycyclohexanone dimethylhydrazone and lithiated cyclohexanone phenylimine

Cited by 77 publications

References 0 publications

μ‐Coordination Chemistry of NO Ligands: Adducts of trans‐Mo(dmpe)2(Cl)(NO) with Lithium Salts

μ‐Coordination Chemistry of NO Ligands: Adducts of trans‐Mo(dmpe)2(Cl)(NO) with Lithium Salts

H2 Activation by Non‐Transition‐Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe3)2

1-Azaallylic Anions in Heterocyclic Chemistry

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μ‐Coordination Chemistry of NO Ligands: Adducts of trans‐Mo(dmpe)₂(Cl)(NO) with Lithium Salts

μ‐Coordination Chemistry of NO Ligands: Adducts of trans‐Mo(dmpe)₂(Cl)(NO) with Lithium Salts

H₂ Activation by Non‐Transition‐Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe₃)₂