σ or π? Bonding interactions in a series of rhenium metallotetrylenes

Autor:	Robert G. Bergman, John Arnold, Iskander Douair, I Joseph Brackbill, Erik T. Ouellette, Laurent Maron, Trevor D. Lohrey, Ambre Carpentier
Přispěvatelé:	Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), NSF [CHE-1465188, 1954612], NIH [S10OD024998], Office of Science, Office of Basic Energy Sciences, of the U.S. DOE [DE-AC02-05CH11231]
Rok vydání:	2021
Předmět:	Inorganic Chemistry Reaction conditions Crystallography Materials science chemistry Salt metathesis reaction chemistry.chemical_element Single bond [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] Rhenium Multiple bonds
Zdroj:	Dalton Transactions Dalton Transactions, 2021, 50 (6), pp.2083-2092. ⟨10.1039/d1dt00129a⟩
ISSN:	1477-9234 1477-9226
Popis:	International audience; Salt metathesis reactions between a low-valent rhenium(I) complex, Na[Re(eta(5)-Cp)(BDI)] (BDI = N,N'-bis (2,6-diisopropylphenyl)-3,5-dimethyl-beta-diketiminate), and a series of amidinate-supported tetrylenes of the form ECI[PhC((NBu)-Bu-t)(2)]) (E = Si, Ge, Sn) led to rhenium metallotetrylenes Re(E[PhC((NBu)-Bu-t)(2)])(eta(5)-Cp)(BDI) (E = Si (1a), Ge (2), Sn (4)) with varying extents of Re-E multiple bonding. Whereas the rhenium-stannylene 4 adopts a sigma-metallotetrylene arrangement featuring a Re E single bond, the rhenium-silylene (1a) and -germylene (2) both engage in pi-interactions to form short Re-E multiple bonds. Temperature was found to play a crucial role in reactions between Na(Re(eta(5)-Cp)(BDI)] and SiCl[PhC((NBu)-Bu-t)(2)], as manipulation of reaction conditions led to isolation of an unusual rhenium-silane, (BDI)Re(mu-eta(5).eta(1)-C5H4)(SiH[PhC((NBu)-Bu-t)(2)]) (1b) and a dinitrogen bridged rhenium-silylene, (eta(5)-Cp)(BDI)Re(mu-N-2)Si(PhC((NBu)-Bu-t)(2)] (1c), in addition to la. Finally, the reaction of Na(Re(eta(5)-Cp)(BDI)] with GeCl2 center dot dioxane led to a rare mu(2)-tetrelido complex, mu(2)-Ge(Re(eta(5)-Cp)(BDI)](2) (3). Bonding interactions within these complexes are discussed through the lens of various spectroscopic, structural, and computational investigations.
Databáze:	OpenAIRE
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