From Chlorogermylenes to Stable Hydroxy- and Siloxy-Germylene−Tungsten Complexes

Bibal, Christine; Mazières, Stéphane; Gornitzka, Heinz; Couret, C.

doi:10.1021/om020187y

Cited by 58 publications

(50 citation statements)

References 28 publications

(20 reference statements)

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“…[2,4] All GeÀO, GeÀ OH and GeÀN bond distances are well within the expected ranges found in related compounds. [26] As previously mentioned, and in a very similar way to that observed in the [V 2 O 2 (pmida) 2 ] 4À binuclear moieties, the two crystallographically independent carboxylate groups appear both coordinated to the Ge 4 + centre in a typical anti-unidentate coordination fashion but, in this case, the CÀ O bonds do not remain equivalent upon coordination. In fact there is clear crystallographic evidence for distinct CÀO bond lengths for the two carboxylate groups (C(3)ÀO(4) 1.309(3), C(3)ÀO (5) 2À complex showing the labelling scheme for all non-hydrogen atoms belonging to the asymmetric unit.…”

Section: Dsupporting

confidence: 68%

X‐ray Diffraction and Solid‐State NMR Studies of a Germanium Binuclear Complex

Mafra

Paz

Shi

et al. 2005

Chemistry A European J

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A compound formulated as (C4H12N2)[Ge2(pmida)2(OH)2] x 4 H2O (where pmida(4-) = N-(phosphonomethyl)iminodiacetate and C4H12N2(2+) = piperazinedium cation), containing the anionic [Ge2(pmida)2(OH)2]2- complex, has been synthesised by the hydrothermal approach and its structure determined by single-crystal X-ray diffraction analysis. Several high-resolution solid-state magic-angle spinning (MAS) NMR techniques, in particular two-dimensional 1H-X(13C,31P) heteronuclear correlation (HETCOR) and 1H-1H homonuclear correlation (HOMCOR) experiments incorporating a frequency-switched Lee-Goldburg (FS-LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic-organic hybrids. We assigned the NMR resonances with the help of C...H and P...H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X-ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry).

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Section: Dsupporting

confidence: 68%

X‐ray Diffraction and Solid‐State NMR Studies of a Germanium Binuclear Complex

Mafra

Paz

Shi

et al. 2005

Chemistry A European J

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“…All their physicochemical data are consistent with their formula. The 119 Sn NMR signal of the tin complex at −80.1 ppm is shifted to low fields in comparison with the signal of its parent stannylene (−280 ppm), indicating that the tin atom is basically fourcoordinate.…”

Section: Iron Complexes L 2 (Cl)mfe(co) 4 M = Ge Snmentioning

confidence: 95%

“…The 119 Sn NMR spectrum of the tin compound exhibits a broad resonance at −280 ppm, indicating that tin in this compound is basically three-coordinated in solution. For the iodogermylene, the 1 H and 13 C NMR (Table 1) chemical shifts are more downfield than those in the other compounds; this may be a result of an increased positive charge on the germanium (or on the ligand backbone) due to a weakly coordinated iodide anion (L 2 Ge· · ·I).…”

Section: (2)mentioning

confidence: 99%

Three‐coordinate divalent Group 14 element derivatives and related compounds

Saur

Alonso

Barrau

2005

Applied Organom Chemis

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INTRODUCTIONThis paper is an overview of a particular part of our systematic investigation of the divalent germanium and tin species focusing on the use in this chemistry of a β-diketiminato ligand with no encumbering aryl groups on the nitrogen. The bidentate three-atom bridging ligand L 2 (L 2 = PhNC(Me)CHC(Me)NPh), by its remarkable stabilizing properties, allows for easy isolation of subvalent germanium and tin compounds and, as such, permits a general insight on the chemistry of such species. The emphasis here will be on the divalent species L 2 (X)M (M = Ge, Sn), the germanechalcogenones L 2 (Cl)Ge Y, the transition- L (n−x) and the cationic ger- IntroductionThe divalent species of Group 14 elements are the heavier carbene analogues; for recent reviews, see Refs 6-10. They are generally transient species. As a general rule, when these species contain unfunctionalized organic ligands, they undergo rapid oligomerization and polymerization. In the last two decades, two principal methods of stabilization have been particularly investigated. Thus, various kinetically and/or thermodynamically stabilized divalent germanium and tin compounds have been isolated in a monomeric state. 1 -5,11 -81 The use of bulky groups bound to the Group 14 element to prevent aggregation permitted the first syntheses of stable monomer divalent species; the most noticeable are the dialkyl-germylene and -stannylene reported by Lappert and co-workers, 12 the first stable monomeric arylgermylene ((Mes * ) 2 Ge (Mes * = 2,4,6-t Bu 3 -phenyl)) described by Du Mont and co-workers, 14 and the well-known aryl-germylene and -stannylene Tbt(Tip)M 14 (M 14 = Ge, Sn; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Tip = 2,4,6-i Pr 3 -phenyl) of Okazaki and co-workers. 25,29The ligand backbone may also play an important role in improving stability. Thus, the presence of ligands with donor side arms on the germanium or the tin element can (by transfer of electron density) reduce the deficit on 37 is, to our knowledge, the first example of an intramolecular base stabilized homoleptic dialkylgermylene. Various amino-, phosphino-, thioalkoxy-, alkoxy-and aryloxy-divalent species have also been isolated in monomeric form owing to this method of stabilization; one should mention in particular the studies of Jutzi and co-workers, 28,32,54,71 Veith and coworkers, 15,18,40,66 Parkin and co-workers, 67 Jurkschat and co-workers, 77,78 Dias and co-workers 31,35,42,69,80,81 and Roesky and co-workers. Main Group Metal Compounds -5Although a large number of homoleptic divalent germanium and tin species have been isolated using these concepts of stabilization, there are fewer examples of heteroleptic compounds having been reported, though the first functional heteroleptic germylenes R(Cl)Ge (R = Et, Ph) were obtained as viscous oils in the 1970 by our group.6 Few solidstate structures of such heteroleptic compounds have been described. Noteworthy examples are in the area of thermodynamic stabilization, the acetylacetonatogermylene R(I)Ge (R = OC (Me) 46...

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“…The mixed ligand germylene compound Ge(Ar ‡ )(N{SiMe 3 } 2 ) (102) (Ar ‡ = 2,6-{CH 2 NEt 2 } 2 C 6 H 3 ) was shown by X-ray diffraction to contain only one Ge· · ·N interaction with the aryl-substituents, resulting in a 3-coordinate Ge centre [89]. Reaction with W(CO) 5 (THF) afforded the expected adduct containing a Ge-W bond, which was subjected to hydrolysis to afford the corresponding hydroxyl-compound, Ge(Ar ‡ )(OH)(W{CO} 5 ) via loss of the amine.…”

Section: Germaniummentioning

confidence: 99%

The role of the bis-trimethylsilylamido ligand, [N{SiMe3}2]−, in main group chemistry. Part 2: Structural chemistry of the metallic p-block elements

Coles

2015

Coordination Chemistry Reviews

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From Chlorogermylenes to Stable Hydroxy- and Siloxy-Germylene−Tungsten Complexes

Cited by 58 publications

References 28 publications

X‐ray Diffraction and Solid‐State NMR Studies of a Germanium Binuclear Complex

X‐ray Diffraction and Solid‐State NMR Studies of a Germanium Binuclear Complex

Three‐coordinate divalent Group 14 element derivatives and related compounds

The role of the bis-trimethylsilylamido ligand, [N{SiMe3}2]−, in main group chemistry. Part 2: Structural chemistry of the metallic p-block elements

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