Disilyne with a silicon-silicon triple bond: A new entry to multiple bond chemistry

Sekiguchi, Akira

doi:10.1351/pac200880030447

Cited by 92 publications

(17 citation statements)

References 88 publications

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“…The preparation and characterization of triply bonded heavier main group element (E 14 = Si, Ge, Sn, and Pb) molecules (i.e., RE 14 ≡E 14 R) is a popular field of study in inorganic chemistry [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ]. From the valence electron viewpoint, the triply bonded RE 13 ≡E 15 R compound is isoelectronic to the RE 14 ≡E 14 R species.…”

Section: Introductionmentioning

confidence: 99%

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Mei

2017

Molecules

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Three computational methods (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp) were used to study the effect of substitution on the potential energy surfaces of RTl≡PR (R = F, OH, H, CH3, SiH3, SiMe(SitBu3)2, SiiPrDis2, Tbt (=C6H2-2,4,6-(CH(SiMe3)2)3), and Ar* (=C6H3-2,6-(C6H2-2, 4,6-i-Pr3)2)). The theoretical results show that these triply bonded RTl≡PR compounds have a preference for a bent geometry (i.e., ∠R⎼Tl⎼P ≈ 180° and ∠Tl⎼P⎼R ≈ 120°). Two valence bond models are used to interpret the bonding character of the Tl≡P triple bond. One is model [I], which is best described as TlP. This interprets the bonding conditions for RTl≡PR molecules that feature small ligands. The other is model [II], which is best represented as TlP. This explains the bonding character of RTl≡PR molecules that feature large substituents. Irrespective of the types of substituents used for the RTl≡PR species, the theoretical investigations (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) demonstrate that their Tl≡P triple bonds are very weak. However, the theoretical results predict that only bulkier substituents greatly stabilize the triply bonded RTl≡PR species, from the kinetic viewpoint.

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Section: Introductionmentioning

confidence: 99%

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Mei

2017

Molecules

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“…This is perhaps surprising considering the rapid expansion of the chemistry of compounds containing p-block elements in very low oxidation states in recent decades. [1] That is not to say that low-oxidation-state Group 2 complexes were not known to be capable of existence under extreme conditions. In the case of magnesium, this has been proven by the spectroscopic characterization of monomeric magnesium(I) compounds such as Mg I (NC) in deep space.…”

Section: Introductionmentioning

confidence: 99%

β‐Diketiminate‐Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis, Characterization, Adduct Formation, and Reactivity Studies

Bonyhady

Jones

Nembenna

et al. 2010

Chemistry A European J

406

231

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The preparation and characterization of a series of magnesium(II) iodide complexes incorporating beta-diketiminate ligands of varying steric bulk and denticity, namely, [(ArNCMe)(2)CH](-) (Ar=phenyl, ((Ph)Nacnac), mesityl ((Mes)Nacnac), or 2,6-diisopropylphenyl (Dipp, (Dipp)Nacnac)), [(DippNCtBu)(2)CH](-) ((tBu)Nacnac), and [(DippNCMe)(Me(2)NCH(2)CH(2)NCMe)CH](-) ((Dmeda)Nacnac) are reported. The complexes [((Ph)Nacnac)MgI(OEt(2))], [((Mes)Nacnac)MgI(OEt(2))], [((Dmeda)Nacnac)MgI(OEt(2))], [((Mes)Nacnac)MgI(thf)], [((Dipp)Nacnac)MgI(thf)], [((tBu)Nacnac)MgI], and [((tBu)Nacnac)MgI(DMAP)] (DMAP=4-dimethylaminopyridine) were shown to be monomeric by X-ray crystallography. In addition, the related beta-diketiminato beryllium and calcium iodide complexes, [((Mes)Nacnac)BeI] and [{((Dipp)Nacnac)CaI(OEt(2))}(2)] were prepared and crystallographically characterized. The reductions of all metal(II) iodide complexes by using various reagents were attempted. In two cases these reactions led to the magnesium(I) dimers, [((Mes)Nacnac)MgMg((Mes)Nacnac)] and [((tBu)Nacnac)MgMg((tBu)Nacnac)]. The reduction of a 1:1 mixture of [((Dipp)Nacnac)MgI(OEt(2))] and [((Mes)Nacnac)MgI(OEt(2))] with potassium gave a low yield of the crystallographically characterized complex [((Dipp)Nacnac)Mg(mu-H)(mu-I)Mg((Mes)Nacnac)]. All attempts to form beryllium(I) or calcium(I) dimers by reductions of [((Mes)Nacnac)BeI], [{((Dipp)Nacnac)CaI(OEt(2))}(2)], or [{((tBu)Nacnac)CaI(thf)}(2)] have so far been unsuccessful. The further reactivity of the magnesium(I) complexes [((Mes)Nacnac)MgMg((Mes)Nacnac)] and [((tBu)Nacnac)MgMg((tBu)Nacnac)] towards a variety of Lewis bases and unsaturated organic substrates was explored. These studies led to the complexes [((Mes)Nacnac)Mg(L)Mg(L)((Mes)Nacnac)] (L=THF or DMAP), [((Mes)Nacnac)Mg(mu-AdN(6)Ad)Mg((Mes)Nacnac)] (Ad=1-adamantyl), [((tBu)Nacnac)Mg(mu-AdN(6)Ad)Mg((tBu)Nacnac)], and [((Mes)Nacnac)Mg(mu-tBu(2)N(2)C(2)O(2))Mg((Mes)Nacnac)] and revealed that, in general, the reactivity of the magnesium(I) dimers is inversely proportional to their steric bulk. The preparation and characterization of [((tBu)Nacnac)Mg(mu-H)(2)Mg((tBu)Nacnac)] has shown the compound to have different structural and physical properties to [((tBu)Nacnac)MgMg((tBu)Nacnac)]. Treatment of the former with DMAP has given [((tBu)Nacnac)Mg(H)(DMAP)], the X-ray crystal structure of which disclosed it to be the first structurally authenticated terminal magnesium hydride complex. Although attempts to prepare [((Mes)Nacnac)Mg(mu-H)(2)Mg((Mes)Nacnac)] were not successful, a neutron diffraction study of the corresponding magnesium(I) complex, [((Mes)Nacnac)MgMg((Mes)Nacnac)] confirmed that the compound is devoid of hydride ligands.

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“…83 4.3.2 Element-element bonds. 26f,g, 86 The near coplanar arrangement of the NSiCGe and Ge 2 N 2 units prevents Ge-Ge multiple bonding, and DFT calculations show the Ge-Ge single bond possesses considerable p-character (92.8%). 26f,g,84 Me 3 Si(Ar*)NGe(Cl) (113) is reduced using half an equivalent of the magnesium(I) dimer [( Mes Nacnac)Mg] 2 to yield Me 3 Si(Ar*)NGeGeN(Ar*)SiMe 3 (114, Fig.…”

Section: Group 14 Complexesmentioning

confidence: 99%

Extremely bulky amide ligands in main group chemistry

Kays

2016

Chem. Soc. Rev.

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The search for extremely sterically demanding monodentate amide ligands to access main group complexes in low-coordination numbers and highly reactive bonding modes is an area of intense research interest. The recent development of three classes of sterically demanding, monodentate amide ligands - the m-terphenyl anilides [N(R){C6H3Ar2-2,6}](-) (Ar = aryl, R = H, methyl, silyl), substituted carbazol-9-yl and the extremely bulky amides [N(R)(Ar')](-) (Ar' = 2,6-{C(H)Ph2}-4-R'-C6H2, R = silyl, aryl, silyloxy, R' = alkyl) is facilitating the isolation of stable species with new coordination modes for the main group elements. These compounds are of fundamental importance not only from the investigation of their structure and bonding, but also the investigation of their reactivity highlights the potential for small molecule activation chemistry under mild conditions and applications in catalysis. This review reports on the recent developments for these compounds with emphasis on their synthesis, structure and reactivity.

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Disilyne with a silicon-silicon triple bond: A new entry to multiple bond chemistry

Cited by 92 publications

References 88 publications

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

β‐Diketiminate‐Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis, Characterization, Adduct Formation, and Reactivity Studies

Extremely bulky amide ligands in main group chemistry

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