Heterocarbenoids of germanium and tin and their polyhedral oxidation products: The case for thermodynamic product control in Group 14 chalcogenides

Schranz, Ingo; Grocholl, Luke; Carrow, Christopher J.; Stahl, Lothar; Staples, Richard J.

doi:10.1016/j.jorganchem.2007.12.031

Cited by 21 publications

(17 citation statements)

References 67 publications

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“…In contrast to its non-solvated analogue reported by Wright et al, 26 Figure 1G). 7 The 119 Sn NMR spectrum of 20 showed signal at δ = 430.9 ppm, which is also consistent with the proposed structure.…”

Section: Figuresupporting

confidence: 83%

“…7 Li NMR spectra showed one signal in each case at δ = 1.10 (2), 1.1 (4), 1.4 (5), 0.0 (5a) and 0.2 ppm (6), all values being comparable to those found in related compounds. 10 Similarly, one signal was detected for each compound in corresponding 31 P NMR spectra [δ = 89.7 (2), 95.5 (4), 139.4 (5), 129.8 (5a) and 127.7 ppm (6)], that are significantly low-field shifted in comparison with starting phosphanes [δ = 41.6 for PhP(NHt-Bu) 2 , 58.0 for PhP(NHt-Bu)(NHDip) and 81.8 ppm for t-BuP(NHDip) 2 ].…”

Section: Methodssupporting

confidence: 73%

“…It is possible to isolate (depending on the stoichiometry) both monolithium and dilithium compounds 2-6, the structure of the dimeric dilithium compound {[PhP(Nt-Bu) 2 ]Li 2 } 2 (1) was reported earlier. 9a All compounds were characterized by 1 H, 7 Li, 13 C and 31 P NMR spectroscopy and molecular structures of 2-4 and 5…”

Section: Resultsmentioning

confidence: 99%

“…6 Noteworthy, germylenene and stannylene cis-[P(-Nt-Bu) 2 P(t-BuN) 2 ]E ( Figure 1G), formally dimers of corresponding bis(imino)phosphides F, were prepared by the conversion of dilithio-precursors and metal(II) chlorides, but their structures were not described. 7 Possible reactivity of germylenes and stannylenes of the type D has recently been investigated theoretically. 8 To enrich the knowledge about germylenes and stannylenes stabilized within the N 2 PE ring systems, we report here on the reactivity of mono-and dilithium derivatives of selected ligand-precursors with GeCl 2 .dioxane and SnCl 2 .…”

Section: Introductionmentioning

confidence: 99%

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Germylenes and stannylenes stabilized within N₂PE rings (E = Ge or Sn): combined experimental and theoretical study

et al. 2016

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The deprotonation of aminophosphanes PhP(NHR)2 (R = t-Bu or Dip; Dip = 2,6-i-Pr2C6H3) and t-BuP(NHDip)2 using n-BuLi gave, depending on the stoichiometry, both the dilithium compounds {[PhP(Nt-Bu)2]Li2}2 (), [PhP(Nt-Bu)(NDip)]Li2·(Et2O) (), [t-BuP(NDip)2]Li2·(Et2O)2 () and [t-BuP(NDip)2]Li2·(tmeda)2 (), and the monolithium compounds [PhP(NHt-Bu)(NR)]Li·(tmeda) (R = t-Bu , Dip ) and [t-BuP(NHDip)(NDip)]Li·(tmeda) (). Treatment of , and with GeCl2·dioxane or SnCl2 in a 1 : 1 stoichiometric ratio gave the corresponding tetrylenes [PhP(Nt-Bu)2]E (E = Ge , Sn ), [PhP(Nt-Bu)(NDip)]Ge () and [t-BuP(NDip)2]E (E = Ge , Sn ). The heteroleptic germylene [Ph(H)P(Nt-Bu)2]GeCl () was obtained by the reaction of the monolithium compound [PhP(NHt-Bu)(Nt-Bu)]Li·(tmeda) () with GeCl2·dioxane in a 1 : 1 stoichiometric ratio, as a result of a spontaneous NH → PH tautomeric shift in the ligand backbone. In contrast, an analogous reaction with SnCl2 produced only stannylene along with the PhP(NHt-Bu)2 starting material, suggesting scrambling of the ligands rather than a NH → PH tautomeric shift. Finally, heating in solution led to P-C bond cleavage and formation of the bis(imino)phosphide [DipNPNDip]Li·(tmeda) (). The reaction of with GeCl2·dioxane, SnCl2 or PbCl2 in a 2 : 1 stoichiometric ratio yielded the unprecedented tetrylenes [DipNPNDip]2E (E = Ge , Sn and Pb ), in which the tetrylene center is incorporated within two N2PE rings. Treatment of the monolithium compound with n-BuLi and K (or KC8) gave [t-BuNPNt-Bu]Li·(tmeda) () and{[t-BuNPNt-Bu]K(tmeda)}2 (), respectively. In contrast to the reaction with , similar reactions of with GeCl2·dioxane and SnCl2 resulted in the known compounds cis-[P(μ-Nt-Bu)2P(t-BuN)2]E (E = Ge, Sn); evidently the t-Bu groups do not provide sufficient steric shielding to protect the bis(imino)phosphide backbone as in the case of . The bonding situation in a set of selected compounds (, ) has been subjected to a theoretical survey with particular emphasis on the nature of the bonding between the ligand and the central metal and the bonding within the NPN core of the ligand, showing significant differences among the studied complexes.

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Section: Figuresupporting

confidence: 83%

Section: Methodssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Germylenes and stannylenes stabilized within N₂PE rings (E = Ge or Sn): combined experimental and theoretical study

et al. 2016

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“…The Ge–O bond lengths are similar to those of the corresponding bonds in {[MeSi(μ‐N t Bu) 2 SiMe( t BuN) 2 ]Ge(μ‐O)} 2 [1.809(4) and 1.825(4) Å]5 and in {[P(μ‐N t Bu) 2 P( t BuN) 2 ]Ge(μ‐O)} 2 [1.78(1) and 1.84(1) Å] 23. The Ge–X(ax) bond is, as expected, longer than the Ge–X(eq) [X = O ( 7a , b ), X = S ( 8 )] bond in the same molecule for the Ge atom in the trigonal‐bipyramidal environment.…”

Section: Results and Discussion Germylene Synthesismentioning

confidence: 99%

Stabilized Germylenes Based on Diethylenetriamines and Related Diamines: Synthesis, Structures, and Chemical Properties

et al. 2012

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A series of novel, low‐valent germanium compounds 2a–2j based on four diethylenetriamines 1a–1d, (methyl)bis(pyrrol‐2‐ylmethyl)amine (1e), N,N′‐(sulfanediyldibenzene‐2,1‐diyl)bis(pentafluoroaniline) (1f), N,N′‐(oxydibenzene‐2,1‐diyl)bis(pentafluoroaniline) (1g), and (pentafluorophenyl)amines 1i and 1j have been obtained either by the reaction of Ge[N(SiMe3)2]2 with various diamines (1a–1e) or by the metathesis reaction of [GeCl2·dioxane] with lithium amides. The oxidative insertion (with halogenation reagents, MeI, disulfides), [1+4] cycloaddition, and oxidation reactions of the synthesized germylenes were investigated. The compositions and structures of the novel compounds were established by elemental analysis, 1H and 13C NMR spectroscopy, and X‐ray diffraction analysis (germylenes 2b, 2i, 2j, Ge4+ compounds 5b, 7a, 7b, 8, 10, 11). All the synthesized germylenes are monomeric.

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Bis(amido)diazadiarsetidinide and Amido(imino)arsenide Complexes of Divalent Metals

Ritter

Hänisch

2021

Eur J Inorg Chem

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The Mg and Ca complexes of the tert‐butyl substituted bis(amido)diazadiarsetidinides [{(tBuNAs)2(tBuN)2}M(thf)2] (M=Mg (1), Ca (6)) were prepared by addition of nBu‐secBuMg or [{(p‐tBu)(C6H4)CH2}2Ca] to [(tBuNAs)2(tBuNH)2] (Ia). Upon evaporation of coordinating THF, 1 is selectively converted to the amido(imino)arsenide complex [Mg{As(NtBu)2}2] (2) whereas 6 decomposes to several products under these conditions. Hydrolysis of 2 with H2O yields the hitherto unknown compound As(NHtBu)3 (3) whereas hydrolysis of Ia leads to the formation of the oxygen bridged bis(amidodiazadiarsetidine) [O{(tBuNH)(tBuNAs)2}2] (4). Reaction of 2 with 3 yields the heteroleptic Mg complex with an amido(imino)arsenide and a bis(amido)diazadiarsetidinide ligand [{(tBuNAs)2(NHtBu)(NtBu)}Mg{As(NtBu)2}] (5). The homologous Ca compound (7) was obtained by conversion of Ia with Ca(hmds)2 (hmds=N(SiMe3)2). Finally, the tetrylene complexes [E{(tBuNAs)2(tBuN)2}] (E=Ge (8), Sn (9), Pb (10)) were prepared by either conversion of Ia with E(hmds)2 for E=Sn, Pb or by addition of the dichlorides of Ge and Sn to [(tBuNAs)2(tBuNLi)2] (Ib). All compounds were characterised by NMR and IR spectroscopy, mass spectrometry and single crystal x‐ray diffraction for 1, 2, 4, 5, 6 and 10.

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Heterocarbenoids of germanium and tin and their polyhedral oxidation products: The case for thermodynamic product control in Group 14 chalcogenides

Cited by 21 publications

References 67 publications

Germylenes and stannylenes stabilized within N₂PE rings (E = Ge or Sn): combined experimental and theoretical study

Germylenes and stannylenes stabilized within N₂PE rings (E = Ge or Sn): combined experimental and theoretical study

Stabilized Germylenes Based on Diethylenetriamines and Related Diamines: Synthesis, Structures, and Chemical Properties

Bis(amido)diazadiarsetidinide and Amido(imino)arsenide Complexes of Divalent Metals

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Heterocarbenoids of germanium and tin and their polyhedral oxidation products: The case for thermodynamic product control in Group 14 chalcogenides

Cited by 21 publications

References 67 publications

Germylenes and stannylenes stabilized within N2PE rings (E = Ge or Sn): combined experimental and theoretical study

Germylenes and stannylenes stabilized within N2PE rings (E = Ge or Sn): combined experimental and theoretical study

Stabilized Germylenes Based on Diethylenetriamines and Related Diamines: Synthesis, Structures, and Chemical Properties

Bis(amido)diazadiarsetidinide and Amido(imino)arsenide Complexes of Divalent Metals

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Germylenes and stannylenes stabilized within N₂PE rings (E = Ge or Sn): combined experimental and theoretical study

Germylenes and stannylenes stabilized within N₂PE rings (E = Ge or Sn): combined experimental and theoretical study