Copper(I) Complexes of Anionic Tridentate CNC Pincer Ligands

Abstract

New monoanionic CNC pincer ligands, [N{SiMe2CH2(RIm)}2]– (R = tBu, iPr, Ph) featuring three different N‐heterocyclic carbenes and a disilylamido moiety is reported. Treatment of the lithium salt of [N{SiMe2CH2(RIm)}2]– with CuIOTf afforded the corresponding copper complexes [N{SiMe2CH2(RIm)}2]Cu in 41–56 % yield. X‐ray crystal structures of [N{SiMe2CH2(RIm)}2]Cu show that they are monomeric and feature three‐coordinate, pseudo T‐shaped copper(I) sites. The X‐ray crystal structure of one of the precursor lithium complexes, [N{SiMe2CH2(tBuIm)}2]Li is also presented.

Mercury(II) Complexes of Anionic N-Heterocyclic Carbene Ligands: Steric Effects of the Backbone Substituent

“…Furthermore, to our knowledge, mercury(II) complexes of anionic N -herterocyclic carbene ligands, such as maloNHC, have not been investigated. As a continuation of our interest in the NHCs and their metal chemistry [ 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 ], we have set out to probe the use of anionic N -heterocyclic carbene ligands in mercury chemistry. In particular, we describe the synthesis and spectroscopic data of three new mercury(II) complexes ( Figure 1 ), (Me-maloNHC Dipp )HgCl ( 1b ), ( t -Bu-maloNHC Dipp )HgCl ( 2b ) and ( t -Bu-maloNHC Dipp )HgMe ( 2c ), involving a bulkier maloNHC.…”

C–H⋯C hydrogen bond and alkali metal C⋯Z⋯C (Z = Li, Na, K) analogues –N-heterocyclic carbenes in coordination spheres of protons and alkali metal cations: crystal structures and theoretical analysis

“…4b shows a fragment of the crystal structure of (3,3′-di- t -butyl-1,1′-(2,2,4,4-tetramethyl-3-aza-2,4-disilapentane-1,5-diyl)bis(imidazol-2-ylidene))-lithium (refcode TUHXIG). 55 The lithium cation is connected here with two NHC species and additionally with a nitrogen centre. The C–Li–C angle (carbon centres are those of two NHC species being in contact with the Li cation) is equal to 145.2°.…”

“…4 Fragments of crystal structures of (a) bis(μ-bis(trimethylsilyl)amido)-(1,3-diethyl-4,5-dimethyl-imidazol-2-ylidene)-dilithium (refcode NEDWEB), 53 and (b) (3,3′-di-t-butyl-1,1′-(2,2,4,4-tetramethyl-3-aza-2,4disilapentane-1,5-diyl)bis(imidazol-2-ylidene))-lithium (refcode TUHXIG). 55 Fig. 5 Fragment of the crystal structure of (η 5 -1,2,4-tris(trimethylsilyl) cyclopentadienyl)-(1,3-di-t-butylimiazol-2-yl)-lithium (MALRAS).…”

Nickel(II) carbonyl, ammonia, and acetonitrile complexes supported by a pyridine dipyrrolide pincer ligand

“…We have been working on tridentate, nitrogen-based ligands such as tris(pyrazolyl)borates with a preference for facial coordination for several years (Dias & Lovely, 2008;Dias et al, , 1996Dias & Lu, 1995). This paper describes results from our efforts to expand the ligand repertoire to include tridentate ligands with a preference for meridional geometry (Adiraju et al, 2020) at transition-metal ions in our laboratory. In particular, we describe the synthesis and use of a pyridine dipyrrolide pincer ligand bearing tolyl substituents, (Pramanik et al, 2014;Pramanik, 2015) and its chemistry with nickel(II) featuring CO, NH 3 and NCMe molecules (Fig.…”