Reactivity of Cu(I) Nacnac Complexes Toward Polypnictogen Compounds

Abstract

The nacnac Cu(I) compound [LCu(MeCN)] (2) (L = [{N-(C 6 H 3 Me 2 -2,6)C(Me)} 2 CH] − ) was reacted with complexes containing aromatic cyclo-E 5 ([Cp*Fe(η 5 -E 5 )], E = P (1a), As (1b), Cp* = η 5 -C 5 Me 5 ), cyclo-P 4 ([Cp‴Co(η 4 -P 4 )] (3), Cp‴ = η 5 -C 5 H 2 t Bu 3 ) and cyclo-E 3 ligands ([Cp‴Ni(η 3 -E 3 )], E = P (4a), As (4b)) yielding the heterometallic complexes [(Cp*Fe)(μ,η 5:2 -E 5 )(LCu)] (E = P (5a), As (5b)), [(Cp*Fe)(μ 3 ,η 5:2:1 -E 5 )(LCu) 2 ] (E = P (6a), As (6b)), [(Cp‴Co)(μ,η 4:2 -P 4 )(LCu)] ( 7), [(Cp‴Co)(μ 3 ,η 4:2:1 -P 4 )(LCu) 2 ] (8), and [(Cp‴Ni)(μ,η 3:2 -E 3 )(LCu)] (E = P (9a), As (9b)). These complexes are rare examples of the coordination of a group 11 metal to aromatic cyclo-E n (E = P, As; n = 3−5) ligands. All products were comprehensively characterized by crystallographic and spectroscopic methods. Their dynamic behavior in solution was studied by VT (variable-temperature) NMR spectroscopy, and their electronic structures were elucidated by DFT calculations.

Reactivity of E4 (E4=P4, As4, AsP3) towards Low‐Valent Al(I) and Ga(I) Compounds

“…temperature, stoichiometry), the reaction of 2 with As 4 only leads to 4 b . [14] In comparison with the lighter homolog phosphorus, the reaction of 2 with white phosphorus in a 1 : 0.75 ratio at 180 °C [15] leads to the formation of 4 a and [(LGa) 2 (P n )] (n=4, 6, 8, 12, 14, 16). [12] Freshly dissolved 3 b in C 6 D 6 was characterized by 1 H NMR spectroscopy at room temperature, showing one set of signals for the two equivalent nacnac ligands.…”

“…temperature, stoichiometry), the reaction of 2 with As 4 only leads to 4 b. [14] In Scheme 2. Reaction of As 4 and AsP 3 with 1 and 2 (dipp = 2,6-diisopropylphenyl).…”

“…Even after changing the reaction conditions (e.g. temperature, stoichiometry), the reaction of 2 with As 4 only leads to 4 b [14] . In comparison with the lighter homolog phosphorus, the reaction of 2 with white phosphorus in a 1 : 0.75 ratio at 180 °C [15] leads to the formation of 4 a and [(LGa) 2 (P n )] (n=4, 6, 8, 12, 14, 16) [12] .…”

Probing the Isolobal Relation between Cp′′′NiP3 and White Phosphorus by Experimental Charge Density Analysis

“…The values of the electron density at the BCP are considerably high in comparison with other literature known transition metal-phosphorus bonds. [29,30,31] The positive Laplacians at the BCP indicate intermediate dative bonds.…”

Unusual formation of Ir(III) complexes with non‐symmetrical NacNac ligands: Synthesis, characterization, and evaluation of catalytic activity in transfer hydrogenation reduction reactions

“…NacNac ligands (β‐aminoazadienes) are capable of stabilizing an extensive range of metal ions in different oxidation states. Their advantages include a capacity for high stereo‐electronic tuneability, coordination with group 13 elements, 1 and their ability to chelate Cu(I) 2 as well as to form Ni(I) complexes 3 and unusual alkali metal complexes 4 . As ancillary ligands, they exhibit a metal–ligand cooperative activation 5,6 .…”