Spontaneous Double Hydrometallation Induced by NM Coordination in Organometallic Hydrides of Group 14 Elements

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F16%3A39902108" target="_blank" >RIV/00216275:25310/16:39902108 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/chem.201504947" target="_blank" >http://dx.doi.org/10.1002/chem.201504947</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201504947" target="_blank" >10.1002/chem.201504947</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Spontaneous Double Hydrometallation Induced by NM Coordination in Organometallic Hydrides of Group 14 Elements

Popis výsledku v původním jazyce

Our attempts to synthesise NM intramolecularly coordinated diorganometallic hydrides L2MH2 [M=Si (4), Ge (5), Sn (6)] containing the CH=N imine group (in which L is C,N-chelating ligand {2-[(2,6-iPr(2)C(6)H(3))N=CH]C6H4}(-)) yielded 1,1-bis(2,6-diisopropylphenyl)-2,2-spriobi[benzo[c][1,2]azasilole] (7), 1,1-bis(2,6-diisopropylphenyl)-2,2-spriobi[benzo[c][1,2]azagermole] (8) and C,N-chelated homoleptic stannylene L2Sn (10), respectively. Compounds 7 and 8 are an outcome of a spontaneous double hydrometallation of the two CH=N imine moieties induced by NM intramolecular coordination (M=Si, Ge) in the absence of any catalyst. In contrast, the diorganotin hydride L2SnH2 (6) is redox-unstable and the reduction of the tin centre with the elimination of H-2 provided the C,N-chelated homoleptic stannylene L2Sn (10). Compounds 7 and 8 were characterised by NMR spectroscopy and X-ray diffraction analysis. Because the proposed NM intramolecularly coordinated diorganometallic hydrides L2MH2 [M=Si (4), Ge (5), Sn (6)] revealed two different types of reduction reactions, DFT calculations were performed to gain an insight into the structures and bonding of the non-isolable diorganometallic hydrides as well as the products of their subsequent reactions. Furthermore, the thermodynamic profiles of the different reaction pathways with respect to the central metal atom were also investigated.

Název v anglickém jazyce

Spontaneous Double Hydrometallation Induced by NM Coordination in Organometallic Hydrides of Group 14 Elements

Popis výsledku anglicky

Our attempts to synthesise NM intramolecularly coordinated diorganometallic hydrides L2MH2 [M=Si (4), Ge (5), Sn (6)] containing the CH=N imine group (in which L is C,N-chelating ligand {2-[(2,6-iPr(2)C(6)H(3))N=CH]C6H4}(-)) yielded 1,1-bis(2,6-diisopropylphenyl)-2,2-spriobi[benzo[c][1,2]azasilole] (7), 1,1-bis(2,6-diisopropylphenyl)-2,2-spriobi[benzo[c][1,2]azagermole] (8) and C,N-chelated homoleptic stannylene L2Sn (10), respectively. Compounds 7 and 8 are an outcome of a spontaneous double hydrometallation of the two CH=N imine moieties induced by NM intramolecular coordination (M=Si, Ge) in the absence of any catalyst. In contrast, the diorganotin hydride L2SnH2 (6) is redox-unstable and the reduction of the tin centre with the elimination of H-2 provided the C,N-chelated homoleptic stannylene L2Sn (10). Compounds 7 and 8 were characterised by NMR spectroscopy and X-ray diffraction analysis. Because the proposed NM intramolecularly coordinated diorganometallic hydrides L2MH2 [M=Si (4), Ge (5), Sn (6)] revealed two different types of reduction reactions, DFT calculations were performed to gain an insight into the structures and bonding of the non-isolable diorganometallic hydrides as well as the products of their subsequent reactions. Furthermore, the thermodynamic profiles of the different reaction pathways with respect to the central metal atom were also investigated.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CA - Anorganická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GA15-07091S" target="_blank" >GA15-07091S: Nekatalyzované Hydrosilylace Indukované N→Si Koordinací</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

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Svazek periodika

22

Číslo periodika v rámci svazku

16

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

5620-5628

Kód UT WoS článku

000374017500025

EID výsledku v databázi Scopus

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