Organometallic Probe for the Electronics of Base‐Stabilized Group 11 Metal Cations

Abstract

A number of trimetalloborides have been synthesized through the reactions of base-stabilized coinage metal chlorides with a dimanganaborylene lithium salt in the hope of using this organometallic platform to compare and evaluate the electronics of these popular coinage metal fragments. The adducts of Cu(I), Ag(I), and Au(I) ions, stabilized by tricyclohexylphosphine (PCy3), N-1,3-bis(4-methylphenyl)imidazol-2-ylidene (ITol), or 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene (CAAC), with [{Cp(CO)2Mn}2B](-) were studied spectroscopically, structurally, and computationally. The geometries of the adducts fall into two classes, one symmetric and one asymmetric, each relying on the combined characteristics of both the metal and ligand. The energetic factors proposed as the causes of the structural differences were investigated by ETS-NOCV (extended transition state-natural orbitals for chemical valence) analysis, which showed the final geometry to be controlled by the competition between the tendency of the coinage metal to adopt a higher or lower coordination number and the willingness of the cationic fragment to participate in back-bonding interactions.

A Cyclic Alkyl(amino)carbene as Two‐Atom π‐Chromophore Leading to the First Phosphorescent Linear CuI Complexes

“…We isolated 1 – 3 by following previously reported procedures for related copper(I) CAAC complexes ,. However, we found that 4 – 6 , unlike their stable CAAC Et congeners,, rapidly decompose during the purification and recrystallization processes, despite the use of an inert atmosphere, and even in the solid state, giving 1 – 3 and free CAAC Me ligand. We were able to confirm the assumed identities of 4 – 6 by isolation of some single crystals, which also decomposed after some time, but were sufficiently stable for X‐ray diffraction analysis (see the Supporting Information).…”

“…The compounds [CuX(CAAC Me )] (X=Cl ( 1 ), Br ( 2 ), I ( 3 )), [Cu(CAAC Me ) 2 ]X (X=Cl ( 4 ), Br ( 5 ), I ( 6 ), PF 6 ( 7 )), [Cu(CAAC Me )(N^N)]PF 6 (N^N=2,2′‐bipyridine ( 8 ), 1,10‐phenanthroline ( 9 )), and [Cu 2 (μ‐SPh) 2 (CAAC Me ) 2 ] ( 10 ) were prepared according to Scheme . We isolated 1 – 3 by following previously reported procedures for related copper(I) CAAC complexes ,.…”

“…The compounds [CuX(CAAC Me )] (X=Cl ( 1 ), Br ( 2 ), I ( 3 )), [Cu(CAAC Me ) 2 ]X (X=Cl ( 4 ), Br ( 5 ), I ( 6 ), PF 6 ( 7 )), [Cu(CAAC Me )(N^N)]PF 6 (N^N=2,2′‐bipyridine ( 8 ), 1,10‐phenanthroline ( 9 )), and [Cu 2 (μ‐SPh) 2 (CAAC Me ) 2 ] ( 10 ) were prepared according to Scheme . We isolated 1 – 3 by following previously reported procedures for related copper(I) CAAC complexes ,. However, we found that 4 – 6 , unlike their stable CAAC Et congeners,, rapidly decompose during the purification and recrystallization processes, despite the use of an inert atmosphere, and even in the solid state, giving 1 – 3 and free CAAC Me ligand.…”

“…All synthetic reactions were performed in an Innovative Te chnology Inc. glovebox or under an argon atmosphere using standard Schlenk techniques. 1 H, 13 C{ 1 H}, 19 F, and 31 PNMR spectra were measured either on aB ruker Avance5 00 ( 1 H, 500 MHz; 13 C,125 MHz;19 F,470 MHz;31 P,202 MHz) or on aB ruker Advance 200 ( 1 H, 200 MHz; 19 F, 188 MHz) NMR spectrometer.M ass spectra were recorded on aQ uadrupol Bruker (formerly Varian) 320-MS singlequadrupole mass spectrometer with direct inlet probe (DIP), with the inlet maintained at 70 8C.…”

Copper and Gold Cyclic (Alkyl)(amino)carbene Complexes with Sub‐Microsecond Photoemissions: Structure and Substituent Effects on Redox and Luminescent Properties

“…Copperh alide and pseudo-halide complexes:C opper(I) halide and pseudo-halidec omplexesw ith ligands Me2 L, Et2 La nd Ad L were prepared as shown in Scheme 1, by combining as olution of the respective CAAC ligandsw ith coppers alts in THF,f ollowing procedures previously established for gold halide complexes. [10,11] While this work was in progress, the syntheses of ( Me2 L)CuCl and ( Et2 L)CuClw ere reportedi ndependently; [12] the compounds are included in Scheme 1f or the sake of completeness.A lthough the reactiono f Me2 Lw ith CuCl is essentially quantitative, the yields of ( Me2 L)CuX (X = Br,I )are moderate due to the formationo fi nsoluble by-products. However,h igh yields of the bromo and iodo complexes can be obtained by metathesis of ( Me2 L)CuClw ith NaBr or NaI, respectively.A n excess of Me2 La ffords the 2:1c omplex [( Me2 L) 2 Cu]I.T he halide complexes show good solubility in polar non-protic solvents like dichloromethane, THF, MeCN, DMF or acetonea nd are moderately soluble in toluene or ethanol but insoluble in hexane.…”