Activation of H<sub>2</sub> by a Multiply Bonded Amido–Digermyne: Evidence for the Formation of a Hydrido–Germylene

Hadlington, Terrance J.; Hermann, Markus; Li, Jiaye; Frenking, Gernot; Jones, Cameron

doi:10.1002/anie.201305689

Cited by 158 publications

(174 citation statements)

References 36 publications

(29 reference statements)

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“…[11] Interestingly,t he employmento fa ne ven 2,6) gives aG e-Ge multiple bond, whichi s much shorter (2.357 ) than in L*GeGeL*. [12] The more bulky substituents L + induce ar otationa bout the NÀGe bond due to steric repulsion, whichr educes the N!Ge p donation. Both amido-digermynes L*GeGeL* and L + GeGeL + rapidly react with H 2 in solution and in the solid state at low temperaturesu pt o À10 8C.…”

Section: Introductionmentioning

confidence: 99%

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Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph₂NEENPh₂, (E=Ge, Sn): A Theoretical Study

Zhao

Jones

Frenking

2015

Chemistry A European J

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Quantum chemical calculations of reaction mechanisms for the formal [2+2] addition of ethylene and acetylene to the amido-substituted digermyne and distannyne Ph2N-EE-NPh2 (E = Ge, Sn) have been carried out by using density functional theory at the BP86/def2-TZVPP level. The nature and bonding situations were studied with the NBO method and with the charge and energy decomposition analysis EDA-NOCV. The addition of ethylene to Ph2N-EE-NPh2 takes place through an initial [2+1] addition to one metal atom and consecutive rearrangement to four-membered cyclic species, which feature a weak E-E bond. Rotation about the C-C bond with concomitant rupture of the E-E bond leads to the 1,2-disubstituted ethanes, which have terminal E(NPh2) groups. The overall reaction Ph2N-EE-NPh2+C2H4→(Ph2N)E-C2H4-E(NPh2) has very low activation barriers and is slightly exergonic for E = Ge but slightly endergonic for E = Sn. The analysis of the electronic structure shows that there is charge donation of nearly one electron to the ethylene moiety already in the first part of the reaction. The energy partitioning analysis suggests that the HOMO(Ph2N-EE-NPh2)→LUMO(C2H4) interaction has a similar strength as the HOMO(C2H4)→LUMO(Ph2N-EE-NPh2) interaction. The [2+2] addition of acetylene to Ph2N-EE-NPh2 also takes place through an initial [2+1] approach, which eventually leads to 1,2-disubstituted olefins (Ph2N)E-C2H2-E(NPh2). The formation of the energetically lowest lying conformations of cis-(Ph2N)E-C2H2-E(NPh2), which occurs with very low activation barriers, is clearly exergonic for the germanium and the tin compound. The trans-coordinated isomers of (Ph2N)E-C2H2-E(NPh2) are slightly lower in energy than the cis form but they are separated by a substantial energy barrier for the rotation about the C-C bond. The energy decomposition analysis indicates that the initial reaction takes place under formation of electron-sharing bonds between triplet fragments rather than HOMO-LUMO interactions.

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Section: Introductionmentioning

confidence: 99%

“…[11,12] Thus, diamido substituted digermynesare more reactive than the aryl digermynesA r 'GeGeAr'. [7] Calculations showedt hat amido-digermynes have very small HOMO-LUMO gaps (< 0.8 eV), [12] which is much smaller than the model arylalkyne analogues (ca. 4.0-6.8 eV).…”

Section: Introductionmentioning

confidence: 99%

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph₂NEENPh₂, (E=Ge, Sn): A Theoretical Study

Zhao

Jones

Frenking

2015

Chemistry A European J

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“…[1] Since a number of low-valent germanium compounds are inherently very reactive, [2] their usefulness for small-molecule activation has been gathering great interest in recent years. [1][2][3][4][5] The activation of dihydrogen using digermynes has been demonstrated by the groups of Power, [4] Jones, and Frenking. [5] Thus, a reaction of digermyne [ [5b] The activation of carbon dioxide at room temperature was reported by Roesky and co-workers using a germanium(II) hydride complex…”

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confidence: 99%

Germylene Cyanide Complex: A Reagent for the Activation of Aldehydes with Catalytic Significance

Siwatch

Nagendran

2014

Chemistry A European J

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The first example of a germanium(II) cyanide complex [GeCN(L)] (2) (L=aminotroponiminate (ATI)) has been synthesized through a novel and relatively benign route that involves the reaction of a digermylene oxide [(L)Ge-O-Ge(L)] (1) with trimethylsilylcyanide (TMSCN). Interestingly, compound 2 activates several aldehydes (RCHO) at room temperature and results in the corresponding cyanogermylated products [RC{OGe(L)}(CN)H] (R=H 3, iPr 4, tBu 5, CH(Ph)Me 6). Reaction of one of the cyanogermylated products (4) with TMSCN affords the cyanosilylated product [(iPr)C(OSiMe3 )(CN)H] (7) along with [GeCN(L)] quantitatively, and insinuates the possible utility of [GeCN(L)] as a catalyst for the cyanosilylation reactions of aldehydes with TMSCN. Accordingly, the quantitative formation of several cyanosilylated products [RC(OSiMe3 )(CN)H] (7-9) in the reaction between RCHO and TMSCN by using 1 mol % of [GeCN(L)] as a catalyst is also reported for the first time.

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“…Compound 118 could also be formed from the reactions between 114 and N 2 O or t BuNCO. 91 The UV/visible spectrum for 114 displays absorption bands at l max = 531 nm and 383 nm, 85 whilst 123 exhibits two absorption bands at l max = 399 nm and 472 nm, 91 which are similar to the pp* and n Àn + transitions for multiply bonded digermynes, indicating a significant electronic difference between these systems. 90 For the t BuNCO reaction the by-product t BuNC was not observed, but is rapidly consumed yielding the reductively coupled product [Me 3 Si(Ar*)NGeCQN t Bu] 2 (119).…”

Section: Group 14 Complexesmentioning

confidence: 97%

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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Activation of H₂ by a Multiply Bonded Amido–Digermyne: Evidence for the Formation of a Hydrido–Germylene

Cited by 158 publications

References 36 publications

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph₂NEENPh₂, (E=Ge, Sn): A Theoretical Study

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph₂NEENPh₂, (E=Ge, Sn): A Theoretical Study

Germylene Cyanide Complex: A Reagent for the Activation of Aldehydes with Catalytic Significance

Extremely bulky amide ligands in main group chemistry

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Activation of H2 by a Multiply Bonded Amido–Digermyne: Evidence for the Formation of a Hydrido–Germylene

Cited by 158 publications

References 36 publications

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph2NEENPh2, (E=Ge, Sn): A Theoretical Study

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph2NEENPh2, (E=Ge, Sn): A Theoretical Study

Germylene Cyanide Complex: A Reagent for the Activation of Aldehydes with Catalytic Significance

Extremely bulky amide ligands in main group chemistry

Contact Info

Product

Resources

About

Activation of H₂ by a Multiply Bonded Amido–Digermyne: Evidence for the Formation of a Hydrido–Germylene

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph₂NEENPh₂, (E=Ge, Sn): A Theoretical Study

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph₂NEENPh₂, (E=Ge, Sn): A Theoretical Study