A model intermediate for the nucleophilic substitution of (Cp)2Sn; synthesis and structure of (Cp)(Me3Si)2NSn(µ-Cp)Li·pmdeta [Cp = C5H5, pmdeta =(Me2NCH2CH2)2NMe]

Paver, Michael A.; Russell, Christopher A.; Wright, Dominic S.

doi:10.1039/c39930001349

Cited by 20 publications

(36 citation statements)

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“…Microcrystalline samples of CpNa and mixed CpNa/ CpNaÐTHF were prepared under nitrogen atmosphere and were each flame-sealed in 1.0 mm capillary tubes. Data were collected at several temperature points ranging from T D 123 1 K to 323 (1) 23 Na experiments are equal to the non-selective solution pulse widths after scaling by a factor of I C 1/2 1 .…”

Section: Powder Xrdmentioning

confidence: 99%

“…A Hahn echo pulse sequence was used for all static and MAS (v rot D 10-11 kHz) experiments using rotor-synchronized data collection wherever applicable. To reduce the appearance of nutation distortions in the spectra, 38,48 soft, CT-selective 23 Na /2 pulse widths ranging from 9.0 to 17.5 µs were used. Experiments typically employed a spectral width of 50 kHz, CW 1 H decoupling fields of 50 kHz, recycle delays of 4-6 s, and a collection of 400-2000 and 29 transients at standard and ultrahigh magnetic fields, respectively.…”

Section: Na Nmrmentioning

confidence: 99%

“…27 -32 Owing to substantial advances in solid-state NMR hardware and characterization Investigation of structure and dynamics in sodium metallocenes S117 cation-interactions, which occur in a plenitude of biological systems, and inorganic and organometallic materials. The Cp 0 Na series of complexes are excellent model systems to help one understand the relationships between molecular structure, dynamic motion and 23 Na chemical shifts and quadrupolar parameters. Lastly, CpNa and CpNaÐTHF are often found as an inhomogeneous microcrystalline mixture (vide infra); hence, it is of great interest to have rapid and accurate methods for the identification of these species as well as for any impurities which result from decomposition.…”

Section: Introductionmentioning

confidence: 99%

“…A single-crystal XRD structure for CpNaÐTHF is reported. The sodium EFG and CS tensors at the sodium atom in CpNaÐTHF are determined experimentally, and the previously observed 38 sodium chemical shielding anisotropy (CSA) in CpNa is defined more precisely using solid-state 23 Na NMR data acquired at several magnetic field strengths. Finally, VT solid-state 23 Na NMR data and VT pXRD experiments in combination with detailed computational modelling are used to propose a model for temperature-dependent structural dynamics in CpNa.…”

Section: Introductionmentioning

confidence: 99%

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Investigation of structure and dynamics in the sodium metallocenes CpNa and CpNa·THF via solid-state NMR, X-ray diffraction and computational modelling

et al. 2007

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Solid-state (23) Na NMR spectra of two organometallic complexes, cyclopentadienylsodium (CpNa) and the tetrahydrofuran (THF) solvate of CpNa (CpNa·THF), are presented. Analytical simulations of experimental spectra and calculated (23) Na electric-field gradient (EFG) tensors confirm that both complexes are present in microcrystalline samples of CpNa recrystallized from THF. For the solvate, (23) Na NMR experiments at 9.4 T and 11.7 T elucidate sodium chemical shielding (CS) tensor parameters, and establish that the EFG and CS tensor frames are non-coincident. Single-crystal X-ray diffraction (XRD) experiments are used to determine the crystal structure of CpNa·THF: Cmca (a = 9.3242(15) Å, b = 20.611(3) Å, c = 9.8236(14) Å, α = β = γ = 90° , V = 1887.9(5)Å(3) , Z = 8). For CpNa, (23) Na NMR data acquired at multiple field strengths establish sodium CS tensor parameters more precisely than in previous reports. Variable-temperature (VT) powder XRD (pXRD) experiments determine the temperature dependence of the CpNa unit cell parameters. The combination of (23) Na quadrupolar NMR parameters, pXRD data and calculations of (23) Na EFG tensors is used to examine various models of dynamic motion in the solid state. It is proposed that the sodium atom in CpNa undergoes an anisotropic, temperature-dependent, low frequency motion within the ab crystallographic plane, in contrast with previous models.

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Section: Powder Xrdmentioning

confidence: 99%

Section: Na Nmrmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Investigation of structure and dynamics in the sodium metallocenes CpNa and CpNa·THF via solid-state NMR, X-ray diffraction and computational modelling

et al. 2007

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“…

This review covers the crystallographic data for dimeric tin compounds with one other metal atom centre, following the pattern of the previous reviews on tin coordination and organometallic compounds. The first eight derivatives contain tin with lithium [6][7][8][9][10][11][12][13], with the tin in the +2 oxidation state and lithium in its usual +1 oxidation state. The predominant geometries of the tin and the heteroatom are discussed along with the relationships between atom size, bond distances and bond angles.

…”

mentioning

confidence: 99%

Heterometallic Tin Compounds: Classification and Analysis of Crystallographic and Structural Data: Part 1. Dimeric Derivatives

Holloway¹,

Melnı́k²

2001

Main Group Metal Chemistry

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This review covers the crystallographic data for dimeric tin compounds with one other metal atom centre, following the pattern of the previous reviews on tin coordination and organometallic compounds. Over two hundred and forty such derivatives have been characterised, twenty three with a non-transition heterometal atom, one with an actinide metal and the rest with a transition metal atom. The predominant geometries of the tin and the heteroatom are discussed along with the relationships between atom size, bond distances and bond angles. The occurrences of direct metal-metal bonds, and examples of isomerism are illustrated CONTENTS 0. ABBREVIATIONS 1. DIMERIC COMPOUNDS 2.1 Α-Group (Non-Transition) MetalsCrystallographic and structural data for some twenty three tin heterometallic compounds with sub-group A. or non-transition metals, are summarised in Table 1. These are listed in their Periodic Group order, with the typical metals of each group first, and then the Sn-M distance. The first eight derivatives contain tin with lithium [6][7][8][9][10][11][12][13], with the tin in the +2 oxidation state and lithium in its usual +1 oxidation state. The shortest Sn-Li bond 136 Brought to you by | Purdue University Libraries Authenticated Download Date | 6/11/15 11:28 PM Main Group Metal Chemistry Vol. 24, Nr. 3, 2001 distance is found in a yellow derivative [6] at 277.6(4) pm. Here, three Ph(Bu')CN ligands bridge the lithium and tin atoms via their Ν atoms, with Sn-N-Li bridge angles of 81,5( 1A slightly longer Sn-Li distance of 278.4(4) pm is found in a cyclometalated dimer [7] leid together by bridging Ο atoms of three 2,6diphenylphenoxide ligands, with mean Sn-O-Li bridge angles of 84.5(2)°.Two crystallographically independent molecules within the asymmetric units of Ph3SnLi(pmdeta) [8] differ essentially by degree of distortion. While the Sn(II) atom is coordinated by three phenyl groups, the Li(I) atom utilises the tridentate pmdeta moiety. Four coordination is accomplished by each metal via a direct Sn-Li bond of 286.1(7) and 288.2(7) pm in the respective distortion isomers. Another colourless derivative [9] also contains two crystallographically independent molecules. A direct Sn-Li bond of 289(4) and 297(5) pm, respectively, hold together the N3Sn and LiCb moieties.A lithium atom in the next derivative [ 10] ties two amido groups together to generate an N-donor arrangement which forms part of the N3Sn pyramid, one corner of which is the Sn(II) atom. The structure of a red derivative [11] involves a {(Me3Si)3}2Sn unit coordinated to a LiCl(thf)3 moiety via a chlorine bridge. The tricoordinated Sn(II) atom is also at one corner of a pyramid. A tricoordinated tin atom is also found in a metallocyclic arrangement [12] of a four membered (Sn-P-Li-P) ring with average Sn-P-Li angles of 89.5(7)°.The Sn centre in a sandwich style complex [13] is attached to two distorted η-cp ligands and the planar Ν atom of a (Me3Si)2N group, as seen in Figure 1. The tin atom has a distorted pyramidal geometry, and the cp(Y) ligand h...

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Lead structures in lithium organic chemistry

Stey

Stalke

2004

The Chemistry of Organolithium Compounds

109

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A model intermediate for the nucleophilic substitution of (Cp)₂Sn; synthesis and structure of (Cp)(Me₃Si)₂NSn(µ-Cp)Li·pmdeta [Cp = C₅H₅, pmdeta =(Me₂NCH₂CH₂)₂NMe]

Cited by 20 publications

References 8 publications

Investigation of structure and dynamics in the sodium metallocenes CpNa and CpNa·THF via solid-state NMR, X-ray diffraction and computational modelling

Investigation of structure and dynamics in the sodium metallocenes CpNa and CpNa·THF via solid-state NMR, X-ray diffraction and computational modelling

Heterometallic Tin Compounds: Classification and Analysis of Crystallographic and Structural Data: Part 1. Dimeric Derivatives

Lead structures in lithium organic chemistry

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