Isomerisierung am Cyclotrisilazan‐System – Lithiumsalze und Kontraktionsprodukte

Egert, Ernst; Kliebisch, U.; Klingebiel, Uwe; Schmidt, Dieter

doi:10.1002/zaac.19875480509

Cited by 15 publications

(2 citation statements)

References 16 publications

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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: 73%

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: 73%

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

2006

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“…Detailed studies [17][18][19] have shown that isomerizations of the cyclotrisilazane system depend on both the extent of lithiation as well as the type of additional substituents. Also thermal effects are important.…”

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confidence: 99%

Silazanes plus MCl4-substitution vs. rearrangement reactions

Lehnert

Wagler

Kroke

et al. 2006

Chem Heterocycl Compd

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Silicon‐Nitrogen Ring‐Ring Interconversions

Klingebiel¹

1990

Inorganic Reactions and Methods

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Isomerisierung am Cyclotrisilazan‐System – Lithiumsalze und Kontraktionsprodukte

Cited by 15 publications

References 16 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

Silazanes plus MCl4-substitution vs. rearrangement reactions

Silicon‐Nitrogen Ring‐Ring Interconversions

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Isomerisierung am Cyclotrisilazan‐System – Lithiumsalze und Kontraktionsprodukte

Cited by 15 publications

References 16 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

Silazanes plus MCl4-substitution vs. rearrangement reactions

Silicon‐Nitrogen Ring‐Ring Interconversions

Contact Info

Product

Resources

About

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