Molecular Lattice Fragment of LiI. Crystal Structure and ab Initio Calculations of [LiI(NEt<sub>3</sub>)]<sub>4</sub>

Doriat, Clemens; Köppe, Ralf; Baum, Elke; Stößer, Gregor; Köhnlein, Harald; Schnöckel, Hansgeorg

doi:10.1021/ic9903432

Cited by 12 publications

(7 citation statements)

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“…Somewhat unexpectedly, the nitrogen atom of the terminal phosphide ligand is bound to a Li 2 I 2 fragment generated during the metathesis reaction. The Li−I distances in 8 range from 2.760(10) to 2.804(12) Å and compare with Li−I distances of 2.932(6) and 2.913(7) Å in dimeric Li 2 I 2 (2,6-Me 2 C 5 H 3 N) and 2.822(6) Å in the heterocubane cluster [LiI(NEt 3 )] 4 …”

Section: Resultsmentioning

confidence: 88%

An Intramolecularly Base-Stabilized Diphosphagermylene and Two Unusual Germanium(II) Ate Complexes: A Structural, NMR, and DFT Study

et al. 2005

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The reaction between GeCl 2 ‚dioxane and 1 equiv of {R(C 6 H 4 -2-CH 2 NMe 2 )P}K (5) yields the heteroleptic complex {R(C 6 H 4 -2-CH 2 NMe 2 )P}GeCl (6) [R ) (Me 3 Si) 2 CH]. Treatment of GeI 2 with 2 equiv of the potassium salt 5 gives the homoleptic, intramolecularly basestabilized diphosphagermylene {R(C 6 H 4 -2-CH 2 NMe 2 )P} 2 Ge (7) in good yield. In contrast, treatment of GeI 2 with 2 equiv of {R(C 6 H 4 -2-CH 2 NMe 2 )P}Li (4) in ether reproducibly yields the unusual ate complex {R(C 6 H 4 -2-CH 2 NMe 2 )P} 2 GeLi 2 I 2 (OEt 2 ) 3 ( 8), whereas treatment of GeI 2 or GeCl 2 ‚dioxane with 3 equiv of 5 yields the cage ate complex {R(C 6 H 4 -2-CH 2 NMe 2 )P} 3 -GeK ( 9). The solid-state structures of 7-9 have been determined by X-ray crystallography, and the dynamic behavior of 6-9 in solution has been studied by multielement and variabletemperature NMR experiments. DFT calculations on the model complex {(Me)(C 6 H 4 -2-CH 2 -NMe 2 )P}GeCl (6a) indicate that inversion at germanium via a planar transition state is disfavored [E inv ) 38.5 kcal mol -1 ] with respect to inversion at phosphorus [E inv ) 21.0 kcal mol -1 ]; inversion at germanium is calculated to proceed via an edge-inversion rather than vertex-inversion process. For the model diphosphagermylene {(Me)(C 6 H 4 -2-CH 2 NMe 2 )P} 2 -Ge (7a) the lowest energy process for epimerization is calculated to be inversion at germanium via a pseudo-trigonal bipyramidal intermediate [E inv ) 3.0 kcal mol -1 ]. Inversion at germanium (via a vertex-inversion process) is calculated to have a barrier of 48.0 kcal mol -1 , whereas the barriers to inversion at phosphorus are 24.0 and 18.5 kcal mol -1 for the chelating and terminal phosphorus atoms, respectively.

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Section: Resultsmentioning

confidence: 88%

An Intramolecularly Base-Stabilized Diphosphagermylene and Two Unusual Germanium(II) Ate Complexes: A Structural, NMR, and DFT Study

et al. 2005

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“…Its structure can be described as two unique LiI units that are bridged by the nitrosyl oxygen atoms of three "Mo-(dmpe) 2 (Cl)(NO) ligands". For LiI-containing adducts 1:1 (Li:ligand), 1:2, and 1:3 monomers, [27] 1:1 and 1:2 dimers, [28] a 1:1 tetramer, [29] and ion-pair coordinated species [30] have been reported. A 2:3 adduct of LiI with 2,4,6-trimethylpyridine (tmpy) was found in fact to be a tetramer with the formulation [(LiI) 4 (tmpy) 6 ].…”

Section: Structure Ofmentioning

confidence: 99%

“…In agreement with the higher coordination number of the Li ion in 4, the O-Li distance of 2.040(10) Å is significantly longer than those observed in 2 and 3 [1.944(6) Å and 1.921(6) Å, respectively]. The I-Li bond length of 2.622(16) Å is particularly short compared with other tetracoordinated LiI complexes (usually in the range of 2.70 to 2.95 Å [27][28][29][30][31] ). The transannular Li-Li "contact" is 2.38(3) Å, which is also particularly short [the shortest LiLi distance reported in LiI complexes is 3.575(6) Å [29] and in 3 it is 2.509(5) Å].…”

Section: Structure Ofmentioning

confidence: 99%

“…The I-Li bond length of 2.622(16) Å is particularly short compared with other tetracoordinated LiI complexes (usually in the range of 2.70 to 2.95 Å [27][28][29][30][31] ). The transannular Li-Li "contact" is 2.38(3) Å, which is also particularly short [the shortest LiLi distance reported in LiI complexes is 3.575(6) Å [29] and in 3 it is 2.509(5) Å]. The observation of unusually short Li-halide and Li-Li distances in 4 is similar to that of the structurally analogous complex [(LiBr) 2 (HMPA) 3 -(toluene) 0.5 ].…”

Section: Structure Ofmentioning

confidence: 99%

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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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“…The energetics of formation and stability with respect to LiI were rationalized using density functional calculations. 86…”

Section: Oxygen-and Sulfur-donor Ligandsmentioning

confidence: 99%

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Gorrell

2001

Annu. Rep. Prog. Chem., Sect. A

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Molecular Lattice Fragment of LiI. Crystal Structure and ab Initio Calculations of [LiI(NEt₃)]₄

Cited by 12 publications

References 19 publications

An Intramolecularly Base-Stabilized Diphosphagermylene and Two Unusual Germanium(II) Ate Complexes: A Structural, NMR, and DFT Study

An Intramolecularly Base-Stabilized Diphosphagermylene and Two Unusual Germanium(II) Ate Complexes: A Structural, NMR, and DFT Study

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

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Molecular Lattice Fragment of LiI. Crystal Structure and ab Initio Calculations of [LiI(NEt3)]4

Cited by 12 publications

References 19 publications

An Intramolecularly Base-Stabilized Diphosphagermylene and Two Unusual Germanium(II) Ate Complexes: A Structural, NMR, and DFT Study

An Intramolecularly Base-Stabilized Diphosphagermylene and Two Unusual Germanium(II) Ate Complexes: A Structural, NMR, and DFT Study

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

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Molecular Lattice Fragment of LiI. Crystal Structure and ab Initio Calculations of [LiI(NEt₃)]₄

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