Germylenes and stannylenes

Neumann, Wilhelm P.

doi:10.1021/cr00003a002

Cited by 427 publications

(234 citation statements)

References 54 publications

(88 reference statements)

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“…Noteworthy examples are in the area of thermodynamic stabilization, the acetylacetonatogermylene R(I)Ge (R = OC(Me)CHC(Me)O) obtained by Stobart 4 in 1979 being the first heteroleptic germylene characterized structurally. 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: 94%

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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Section: Methodsmentioning

confidence: 94%

Three‐coordinate divalent Group 14 element derivatives and related compounds

Saur

Alonso

Barrau

2005

Applied Organom Chemis

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“…No cycloadduct between 2,3-dimethyl-1,3-butadiene and dimethylstannylene was obtained. 12 The formation of 1,3,5,2,4,6-trithiatristannin (1) can be explained in terms of trimerization of the initially formed dimethylstannanethione, Me 2 Sn S (8; Scheme 4).…”

Section: Photochemical Reaction Of 127-thiadistannacycloheptane (6)mentioning

confidence: 99%

Synthesis and photochemical reactions of 1,2,7‐chalcogenadistannacycloheptanes

Saito

Iso

Yamada

et al. 2005

Applied Organom Chemis

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1,2,7-Chalcogenadistannacycloheptanes were synthesized by the reactions of 1,4-bis(bromostannyl) butane with appropriate chalcogenation reagents. Irradiation of the 1,2,7-thiadistannacycloheptane with a low-pressure mercury lamp (254 nm) gave 1,3,5,2,4,6-trithiatristannin. Irradiation of 1,3,5,2,4,6-trithiatristannin with a low-pressure mercury lamp in the presence of either cyclotrisiloxane or 2,3-dimethyl-1,3-butadiene gave a complex mixture.

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“…7,8 Germylenoid is a kind of important derivative of germylene, and may have the stronger stability than germylene. Similar to carbenoids 9,10 and silylenoids, 11,12 germylenoids are complexes formed between free germylenes and inorganic salts, which can be expressed as R 1 R 2 GeMX (M = alkali metal, X = halogen).…”

Section: Introductionmentioning

confidence: 99%

Substitution Reactions of the Aluminum Chlorogermylenoid H2GeClAlCl2 with with HF, H2O, NH3, HCl, H2S, and PH3

Yan¹,

Zhang²,

Li³

et al. 2016

ACSi

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Quantum chemical calculations have been performed for the substitution reactions of the aluminum chlorogermylenoid H 2 GeClAlCl 2 with HF, H 2 O, NH 3 , HCl, H 2 S, and PH 3 to get more insights into the reactivity of H 2 GeClAlCl 2 . The theoretical calculated results indicated that the substitution reactions of H 2 GeClAlCl 2 with HF, H 2 O, NH 3 , HCl, H 2 S, and PH 3 proceeded in a concerted manner. There were one transition state and one intermediate which connected the reactants and the products along the potential energy surface. The six substitution reactions of H 2 GeClAlCl 2 with HF, H 2 O, NH 3 , HCl, H 2 S, and PH 3 are compared with the addition reaction s of H 2 Ge with these hydrides. And based on the calculated results we concluded that the substitution reactions of H 2 GeClAlCl 2 with these hydrides involve two steps, one is dissociation onto H 2 Ge with AlCl 3 , and the other is the addition reactions of H 2 Ge with HF, H 2 O, NH 3 , HCl, H 2 S, and PH 3 .

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Germylenes and stannylenes

Cited by 427 publications

References 54 publications

Three‐coordinate divalent Group 14 element derivatives and related compounds

Three‐coordinate divalent Group 14 element derivatives and related compounds

Synthesis and photochemical reactions of 1,2,7‐chalcogenadistannacycloheptanes

Substitution Reactions of the Aluminum Chlorogermylenoid H2GeClAlCl2 with with HF, H2O, NH3, HCl, H2S, and PH3

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