Details

Autor(en) / Beteiligte

• Roselló-Merino, Marta
• Mansell, Stephen M

Titel

Synthesis and reactivity of fluorenyl-tethered N-heterocyclic stannylenesElectronic supplementary information (ESI) available: Additional synthetic details for tBuN(H)C2H4NH2, 1b, 1c and 1d, NMR spectra for all the compounds and additional crystallographic information including the crystal structures of 1a (in P1&cmb.macr;), 1b and 1b·2HCl. CCDC 1424295-1424301, 1431076 and 1441450. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt04060d. Additional resear

Erscheinungsjahr

2016-03

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A fluorenyl (Fl) tethered diamine was synthesised by nucleophilic substitution of (bromoethyl)fluorene with a diisopropylphenyl (Dipp) substituted diamine to give FlC 2 H 4 N(H)C 2 H 4 N(H)Dipp ( 1a ) in good yield (85%). Lithiation of 1a with n -BuLi proceeded with coordination of the Li cation to the aromatic fluorenide ring ( 2 ), and with subsequent equivalents of n -BuLi, the secondary amines were then sequentially deprotonated. A fluorenyl-tethered N-heterocyclic stannylene (NHSn) was synthesised from the reaction of 1a with SnN′′ 2 {N′′ = N(SiMe 3 ) 2 } as a neutral dimeric species ( 5 ), and this was deprotonated with LiN′′ to give the corresponding dianionic fluorenide-tethered NHSn ( 6 ). Reactions of [{Rh(cod)(μ-Cl)} 2 ] with the mono-deprotonated ligand 2 led to the formation of a mixed-donor amide-amine Rh( i ) compound ( 7 ), whereas reactions with the anionic NHSn 6 led to a Rh-fluorenyl complex of low stability with an uncoordinated pendent NHSn arm, which X-ray crystallography showed to be dimeric in the solid state. N-Heterocyclic stannylenes containing a functionalised donor arm have been synthesised using a transamination strategy from [Sn{N(SiMe 3 ) 2 } 2 ] and fluorenyl-tethered diamines.