1,3-Di-tert-butyl-2,2-dimethyl-5,8-diphenyl-1,3,5,6,7,8-hexaaza-2-sila-4-germaspiro[3.4]oct-6-ene

Preut, H.; Obloh, R. C.; Neumann, W. P.

doi:10.1107/s0108270187011296

Cited by 4 publications

(4 citation statements)

References 3 publications

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“…An X-ray diffraction study of 1 confirmed the connectivity; however, the data are not of sufficient quality for reporting accurate structural data. The previously reported germanium tetrazoles were also formed upon treatment of the corresponding germylene with the relevant azides; ,, it is assumed that a germanimine is formed in situ which then reacts with additional azide to form the tetrazole compound.…”

Section: Results and Discussionsupporting

confidence: 58%

Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

et al. 2021

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We report the synthesis of aromatic germanimines [(HMDS) 2 GeNAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-Me 3 C 6 H 2 , Dipp = 2,6-iPr 2 C 6 H 3 ) and an investigation into their associated reactivity. [(HMDS) 2 GeNPh] decomposes above −30 °C, while [(HMDS) 2 GeNDipp] engages in an intramolecular reaction at 60 °C. [(HMDS) 2 GeNMes] was shown to rearrange via a 1,3-silyl migration to give [(HMDS){(SiMe 3 )-(Mes)N}Ge(NSiMe 3 )] in a 1:7 equilibrium mixture at room temperature. These latter germanimines react with unsaturated polar substrates such as CO 2 , ketones, and arylisocyanate via a [2 + 2] cycloaddition pathway.

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Section: Results and Discussionsupporting

confidence: 58%

Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

et al. 2021

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“…29 Nevertheless, the germylene Me 2 Si(N-t-Bu) 2 Ge[N(Ph)N]N(Ph)N] represents a structurally characterized analogue of 12. 30 Noteworthy, several examples of Ge(IV) spiro boramidinates (consisting of two four-membered rings) were reported, but their structures were not determined in the solid state. 31 The Ge-N(boraguanidinate) bond distances fall within a narrow interval 1.8472(13)-1.872(2) Å in 10-12, while the Ge(1)-N(4) and Ge(1)-N(5) bond distances are 1.8447 (19)…”

Section: Reactivity Studies Of the Germylenementioning

confidence: 99%

Synthesis and reactivity of a germylene stabilized by a boraguanidinate ligand

et al. 2016

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“…Comparing the structure to the most similar compound in the literature; XXIII the increased steric interaction between the TMS groups and the mesityl groups can be seen. 44 The similar, though more conformationally free tetrazagermole XXIV has similar Ge-N bond lengths for the tetrazene ligand 1.850 and 1.852 Å XXIV also has the N-N distances in the tetrazene of 1.394 and 1.360 Å, similar to 8. The Ge(1)-N(3) bond distance of 1.816 Å in 8 is longer than that of XXIII (1.808 and 1.812…”

Section: Attempted Synthesis Of [(Naph Tms )Ge(nmes)]mentioning

confidence: 94%

“…Two such germanes are the N-heterocyclic supported compound XXIII and the bis-amide supported germane XXIV. 23,44 These reactions highlight the importance of the use of sufficient steric bulk in both the azide and the germylene to sufficiently kinetically stabilise the desired germanimine.…”

Section: XXmentioning

confidence: 99%

Studies towards the Synthesis of a Heterobimetallic Zirconium Germanium Complex from Imidozirconocenes, Germanimines and Germylenes

Chapple¹

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<p>Early-late transition metal heterobimetallic complexes with direct metal to metal interactions are desirable synthetic targets due to the complementary reactivity of the two different metals present in these compounds. The electron-rich late transition metal (often Rh, Ir, Fe, or Mo), and electron-poor early transition metal create an ideal environment for heterolytic bond cleavage in what is often termed ‘cooperative reactivity’. This project aimed to synthesise a zirconium-germanium heterobimetallic complex based on a known heterobimetallic ligand scaffold; 1. The synthesis of the desired heterobimetallic 1 was attempted using two different synthetic approaches. The first involved the investigating the reactivity between an unsaturated zirconium nitrogen bond (an imidozirconocene) and a germanium(II) source with a lone pair of electrons (known as a germylene). The second approach investigated the reactivity between an unsaturated germanium nitrogen bond (a germanimine) and a zirconium(II) source. In order to have the highest chance of success, a wide range of germanium and zirconium complexes were synthesised. The novel germylenes include [Ge(NAPHTMS)] (NAPHTMS = [1,8-((CH3)3Si)N)2C10H6]) and [Ge(BIANMes)] (BIANMes = [((2,4,6-Me(C6H2)N)2)C12H6)]). These proved to be unreactive towards the imidozirconium species [Cp2Zr(NAr*)(THF)] and [Cp2Zr(NDipp)(THF)] (Ar* = (2,6-(C6H5)2CH)-4-(tBu)C6H2), Dipp = (2,6-((CH3)2CH)C6H3)) as well as other amidozirconocenes. However, within these studies, the mixed coordination germanium species [[Ge(NAPHTMS)Ge(Bu)(NAPHTMS)]-[Li(THF4)]+] and [[Ge(NAPHTMS)Ge(Me)(NAPHTMS)]-[Li(THF4)]+]were synthesised. Density functional theory (DFT) molecular orbital calculations were used to help explain the observed reactivity. With regards to the second approach, routes to new germanimine complexes such as [(HMDS)2Ge(NMes)] ((HMDS) = ((CH3)3Si)2N), Mes = (2,4,6-CH3(C6H3))), were explored, and several methods for generating “Cp2Zr” were examined. Although these conditions proved unsuccessful for generating 1, the reaction between dialkyl zirconocene with azides to form novel zirconocene triazenido complexes was discovered and the sterics affecting the synthesis of new germanimine complexes was investigated.</p>

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1,3-Di-tert-butyl-2,2-dimethyl-5,8-diphenyl-1,3,5,6,7,8-hexaaza-2-sila-4-germaspiro[3.4]oct-6-ene

Cited by 4 publications

References 3 publications

Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

Synthesis and reactivity of a germylene stabilized by a boraguanidinate ligand

Studies towards the Synthesis of a Heterobimetallic Zirconium Germanium Complex from Imidozirconocenes, Germanimines and Germylenes

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