Synthesis and Characterization of the Monomeric Terphenyl−Metal Halides Ge(Cl){C6H3-2,6-Trip2} (Trip = C6H2-2,4,6-i-Pr3) and Sn(I){C6H3-2,6-Trip2} and the Terphenyl−Metal Amide Sn{N(SiMe3)2}{C6H3-2,6-Trip2}

Pu, Lihung; Olmstead, Marilyn M.; Power, Philip P.; Schiemenz, Berthold

doi:10.1021/om980697l

Cited by 114 publications

(82 citation statements)

References 38 publications

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“…[16] Metathetical exchange of 5 with LiC 6 H 3 -2,6-Mes 2 [17] then afforded selectively the arylgermanium(II) chloride 7 a (Scheme 1). Compound 7 b was obtained upon addition of imidazol-2-ylidene 2 to GeCl(C 6 H 3 -2,6-Trip 2 ) (6 b-Ge) [18] in toluene (Scheme 1). The Ge II compounds were isolated in high yields as white, air-sensitive solids.…”

Section: Resultsmentioning

confidence: 99%

“…All solvents were stored in a glove box. SiArHCl 2 [Ar = C 6 H 3 -2,6-Mes 2 (1 a), C 6 H 3 -2,6-Trip 2 (1 b)], [14] Im-Me 4 (2), [13] GeCl 2 (1,4-dioxane), [15] LiC 6 H 3 -2,6-Mes 2 , [17] and GeCl(C 6 H 3 -2,6-Trip 2 ) (6 b-Ge) [18] were prepared according to published procedures and were shown by NMR spectroscopy [33][34][35] and elemental analyses to be pure. The C, H, N analyses of all compounds were carried out three times on an Elementar Vario Micro elemental analyzer.…”

Section: Methodsmentioning

confidence: 99%

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Stable N‐Heterocyclic Carbene Adducts of Arylchlorosilylenes and Their Germanium Homologues

Filippou

Chernov

Blom

et al. 2010

Chemistry A European J

146

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The first N-heterocyclic carbene adducts of arylchlorosilylenes are reported and compared with the homologous germanium compounds. The arylsilicon(II) chlorides SiArCl(Im-Me(4)) [Ar=C(6)H(3)-2,6-Mes(2) (Mes=C(6)H(2)-2,4,6-Me(3)), C(6)H(3)-2,6-Trip(2) (Trip=C(6)H(2)-2,4,6-iPr(3))] were obtained selectively on dehydrochlorination of the arylchlorosilanes SiArHCl(2) with 1,3,4,5-tetramethylimidazol-2-ylidene (Im-Me(4)). The analogous arylgermanium(II) chlorides GeArCl(Im-Me(4)) were prepared by metathetical exchange of GeCl(2)(Im-Me(4)) with LiC(6)H(3)-2,6-Mes(2) or addition of Im-Me(4) to GeCl(C(6)H(3)-2,6-Trip(2)). All compounds were fully characterized. Density functional calculations on ECl(C(6)H(3)-2,6-Trip(2))(Im-Me(4)), where E=Si, Ge, at different levels of theory show very good agreement between calculated and experimental bonding parameters, and NBO analyses reveal similar electronic structures of the two aryltetrel(II) chlorides. The low gas-phase Gibbs free energy of bond dissociation of SiCl(C(6)H(3)-2,6-Trip(2))(Im-Me(4)) (Delta(calcd) degrees=28.1 kJ mol(-1)) suggests that the carbene adducts SiArCl(Im-Me(4)) may be valuable transfer reagents of the arylsilicon(II) chlorides SiArCl.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Stable N‐Heterocyclic Carbene Adducts of Arylchlorosilylenes and Their Germanium Homologues

Filippou

Chernov

Blom

et al. 2010

Chemistry A European J

146

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“…One should also mention the germylenes and stannylenes described by Veith et al 6 and Lappert and co-workers 8 46,68 have been particularly involved in this work. In the area of kinetic stabilization, the main results concern the compounds obtained by Power and co-workers 50 using bulky aryl groups.…”

Section: Methodsmentioning

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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“…Though the novel cationic germanium(II) compound [{( i Pr) 2 ATI}]Ge[CpZrCl 2 (-Cl) 3 ZrCl 2 Cp] (29) was prepared by Dias and co-workers [18], no studies have dealt with cationic germanium(II)-transition metal complexes. The attempted synthesis of cationic germanium(II)-tungsten complex was unsuccessful when [(Ph) 2 DAP]GeOTf (22) was reacted with W(CO) 5 THF afforded the first digermanium(II)-tungsten complex [{(Ph) 2 DAP}GeCl] 2 W(CO) 4 (27) (Scheme 6), but the X-ray structure determination of the dicationic species was not successful.…”

Section: Reactions Of ␤-Diketiminato Germanium(ii) Chloridementioning

confidence: 99%