Synthesis and structural characterization of two-coordinate low-valent 14-group metal complexes bearing bulky bis(amido)silane ligands

Yang, Dan; Guo, Jin; Wu, Huang; Ding, Yuqiang; Zheng, Wenjun

doi:10.1039/c1dt11774b

Cited by 54 publications

(30 citation statements)

References 38 publications

(10 reference statements)

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“…2.03 vs. 2.09 Å) . In the case of the aryl‐substituted congeners [Me 2 Si(NDipp) 2 ] n Sn ( n= 1, 2; Dipp=2,6‐diisopropylphenyl), however, the Sn−N bond lengths of the stannylene and the tin(IV) spiro compound are essentially identical (ca. 2.06 Å).…”

Section: Resultsmentioning

confidence: 99%

“…Compounds 1 Mes Sn and 1 TMS Sn in C 6 D 6 give rise to 119 Sn NMR signals at δ =403 and 589 ppm, respectively, which is in the region typical of diaminostannylenes that lack additional donor interactions . For comparison, values between δ =236 and 536 ppm have been reported for the N‐heterocyclic stannylenes in Table S2 (see the Supporting Information) that contain strictly dicoordinate tin(II) atoms according to the results of X‐ray diffraction studies ( 119 Sn NMR (C 6 D 6 ): [Nap(NSi i Pr 3 ) 2 ]Sn: δ =514 (Nap=naphthalene‐1,8‐diyl), [CH 2 (CH 2 NDipp) 2 ]Sn: 291, trans ‐(CHMeN t Bu) 2 Sn: 454, (CHNMes) 2 Sn: 259, [ o ‐C 6 H 4 (NMes) 2 ]Sn: 236, [R 2 Si(NDipp) 2 ]Sn: 536 and 514 ppm for R= i Pr and Me, respectively). The 119 Sn NMR signals of the acyclic diaminostannylenes [(Me 3 Si) 2 N ] 2 Sn and [(PhMe 2 Si) 2 N ] 2 Sn in C 6 D 6 are located at δ =767 and 501 ppm, respectively.…”

Section: Resultsmentioning

confidence: 99%

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Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone

Oetzel

Weyer

Bruhn

et al. 2016

Chemistry A European J

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We describe ferrocene-based N-heterocyclic germylenes and stannylenes of the type [Fe{(η -C H )NR} E:] (1 RE; E=Ge, Sn; R=neopentyl (Np), mesityl (Mes), trimethylsilyl (TMS)), which constitute the first examples of redox-functionalised N-heterocyclic tetrylenes (NHTs). These compounds are thermally stable and were structurally characterised by means of X-ray diffraction studies, except for the neopentyl-substituted stannylene 1 NpSn, the decomposition of which afforded the aminoiminoferrocene [fc(NHCH tBu)(N=CHtBu)] (2) and the spiro tin(IV) compound (1 Np) Sn (3). DFT calculations show that the HOMO of the NHTs of our study is localised on the ferrocenylene backbone. A one-electron oxidation process affords ions of the type 1 RE . In contrast to the NHC system 1 RC, the localised ferrocenium-type nature of the oxidised form does not compromise the fundamental tetrylene character of 1 RE .

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone

Oetzel

Weyer

Bruhn

et al. 2016

Chemistry A European J

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“…Ever since the syntheses of the first stannylenes by Lappert and co‐workers1 in 1976, N , N′ ‐chelation as exemplified by amidinates and diamidosilanes has been recognized as an advantageous ligand design for stabilizing low‐valent metallic group 14 motifs. [Me 2 Si(NR′) 2 M II ] (M = Ge,2 Sn,3 Pb;4 R′ = t Bu, Dipp, etc. ; a in Scheme ) and [R″C(NR′) 2 M II R] (M = Ge,5 Sn,6 Pb;7 R = Hal, alkyl, amide, etc; R′ = t Bu, SiMe 3 , c Hex, Dipp, etc.…”

Section: Introductionmentioning

confidence: 99%

Manipulation of Phosphorescence Efficiency of Cyclometalated Iridium Complexes by Substituted o‐Carboranes

Lee

Park

et al. 2014

Chemistry A European J

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A series of [(C^N)2 Ir(acac)] complexes [{5-(2-R-CB)ppy}2 Ir(acac)] (3 a-3 g; acac=acetylacetonate, CB=o-carboran-1-yl, ppy=2-phenylpyridine; R=H (3 a), Me (3 b), iPr (3 c), iBu (3 d), Ph (3 e), CF3 C6 H4 (3 f), C6 F5 (3 g)) with various 2-R-substituted o-carboranes at the 5-position in the phenyl ring of the ppy ligand were prepared. X-ray diffraction studies revealed that the carboranyl CC bond length increases with increasing steric and electron-withdrawing effects from the 2-R substituents. Although the absorption and emission wavelengths of the complexes are almost invariant to the change of 2-R group, the phosphorescence quantum efficiency varies from highly emissive (ΦPL ≈0.80 for R=H, alkyl) to poorly emissive (R=aryl) depending on the 2-R group and the polarity of the medium. Theoretical studies suggest that 1) the almost nonemissive nature of the 2-aryl-substituted complexes is mainly attributable to the large contribution to the LUMO in the S1 excited state from an o-carborane unit and 2) the variation in the CC bond length between the S0 and T1 state structures increases with increasing steric (2-alkyl) and electronic effects (2-aryl) of the 2-R substituent and the polarity of the solvent. The solution-processed electroluminescence (EL) devices that incorporated 3 b and 3 d as emitters displayed higher performance than the device based on the parent [(ppy)2 Ir(acac)] complex. Along with the high phosphorescence efficiency, the bulkiness of the 2-R-o-carborane unit is shown to play an important role in improving device performance.

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“…The Pb-N(amido) distances of the two symmetrically independent molecules are in the range of 224.8(7)-232.9 (7) pm and the Pb-N(pyridyl) distances are 250.6(7)-251.6(7) pm. [22] Ph 2 Si(NDipp) 2 Pb: 220.6-226.7 pm, [16] and the observed moderate elongation is due to the presence of additional weak Pb-N(pyridyl) interactions. The Pb-N(pyridyl) distances in compounds 5 and 6 compare well with the data observed in [2-phenyl-3-(2-pyridyl)-1,3-bis(trimethylsilyl)-1-azaallyl]-lead(II) (257.0-262.6 pm).…”

Section: Articlementioning

confidence: 98%

“…Me 2 Si(NtBu) 2 Sn (209.1 pm), [14] Ph 2 Si(NDipp) 2 Sn (206.9-212.0 pm), [15] and Me 2 Si(NDipp) 2 Sn (204.7-209.5 pm). [16] In the case of dimeric compounds {R 2 Si(NRЈ) 2 Sn} 2 with ladder-like structures the terminal Sn-N distances are comparable to those of compound 3, e.g. {Me 2 Si(NtBu) 2 Sn} 2 (210.0 pm), [14] Z.…”

Section: Crystal Structuresmentioning

confidence: 99%

Novel Dinuclear Tin(II) and Lead(II) Compounds with 2-Pyridyl Functionalized Silylamido Ligands

Wagner¹,

Merzweiler

2017

Z. Anorg. Allg. Chem.

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Treatment of R 2 SiCl 2 (R = Me, Ph) with 2-aminopyridine in the presence of NEt 3 led to the formation of the bis(N-2-pyridylamino)silanes R 2 Si{NH(2-Py)} 2 , which were isolated as pale yellow solids. Crystal structure analyses revealed that both compounds exhibit tetrahedrally coordinated silicon atoms which are linked to two 2-pyridylamido moieties and two organyl groups (Me or Ph). As a result of intermolecular hydrogen bonding between the NH groups and the pyridyl N atoms the R 2 Si{NH(2-Py)} 2 molecules are catenated in 938 the solid state. Treatment of R 2 Si{NH(2-Py)} 2 with nBuLi afforded the corresponding amides R 2 Si{NLi(2-Py)} 2 , which were subsequently reacted with MCl 2 (M = Sn, Pb) to give the dinuclear silylamides [{R 2 Si(N-2-Py) 2 M} 2 ]. Both the tin and the lead derivatives exhibit closely related molecular structures, in which the tin (or lead) atoms are linked to two amido N atoms and a pyridyl N atom in a distorted trigonal bipyramidal coordination mode. 939Scheme 2. Synthesis of the Sn and Pb silylamides (3-6).

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Synthesis and structural characterization of two-coordinate low-valent 14-group metal complexes bearing bulky bis(amido)silane ligands

Cited by 54 publications

References 38 publications

Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone

Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone

Manipulation of Phosphorescence Efficiency of Cyclometalated Iridium Complexes by Substituted o‐Carboranes

Novel Dinuclear Tin(II) and Lead(II) Compounds with 2-Pyridyl Functionalized Silylamido Ligands

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