Heterobimetallic Cuprates Consisting of a Redox‐Switchable, Silicon‐Based Metalloligand: Synthesis, Structures, and Electronic Properties

A computationally guided synthetic route to a free silanide derived from tris(3‐methylindol‐2‐yl)methane ([(tmim)Si]−) through nucleophilic substitution on the SiII precursor (Idipp)SiCl2 is reported (Idipp=2,3‐dihydro‐1,3‐bis(2,6‐diisopropylphenyl)‐1H‐imidazol‐2‐ylidene). This approach circumvents the need for strained tetrahedral silanes as synthetic intermediates. Computational investigations show that the electron‐donating properties of [(tmim)Si]− are close to those of PMe3. Experimentally, the [(tmim)Si]− anion is shown to undergo clean complexation to the base metal salts CuCl and FeCl2, demonstrating the potential utility as a supporting ligand.

Section: Methodsmentioning

confidence: 85%

“… Zwitterionic silanides, and the all‐organic analogue described here. R=Me, C 2 H 5 OCH 3 ; D=donor; M=alkali metal or transition metal.…”

Section: Methodsmentioning

confidence: 99%

A Free Silanide from Nucleophilic Substitution at Silicon(II)

Witteman

Evers

Lutz

et al. 2018

“…The SiCu bond length [2.2081(9) Å] in 2 compares well with the Si sp2 Cu distances (2.2412(8) and 2.2458(8) Å) in a lithium bis(disilenyl)cuprate,18 but is less than the 2.43 Å sum of the silicon and copper covalent radii 19. The bent Si‐Cu‐Cl angle (167.35(5)° in 2 ) contrasts with the perfectly linear fragment in [CuCl{μ‐κ 1 Si:κ 3 N‐Si(3,5‐Me 2 pz) 3 Mo(CO) 3 }] − 20. Coordination of CuCl to the L:SiSi:L fragment in 1 affects the structure and bonding of the resulting complex, 2 .…”

Section: Methodsmentioning

confidence: 98%

Dynamic Complexation of Copper(I) Chloride by Carbene‐Stabilized Disilicon

Chen

Wang

Xie

et al. 2014

“…Although DFT calculations predicted only marginal changes of the bonding characteristics within the {MX} fragment upon electronic excitation of the ruthenium‐based metalloligand, some effect of the influence of {MX} on the Ru II /Ru III redox potential was detected with the aid of cyclic voltammetry measurements. Related studies have been perfomed for heterobimetallic cuprates consisting of a redox‐switchable, silicon‐based metalloligand ( VIII ) …”

Section: Introductionmentioning

confidence: 99%

A Redox‐Switchable Germylene and its Ligating Properties in Selected Transition Metal Complexes

Walz

Moos

Garnier

et al. 2016

Self Cite

The synthesis, structure, and full characterization of a redox-switchable germylene based on a [3]ferrocenophane ligand arrangement, [Fc(NMes) Ge] (4), is presented. The mesityl (Mes)-substituted title compound is readily available from Fc(NHMes) (2) and Ge{N(SiMe ) } , or from the dilithiated, highly air- and moisture-sensitive compound Fc(NLiMes) ⋅3 Et O (3) and GeCl . Cyclic voltammetry studies are provided for 4, confirming the above-mentioned view of a redox-switchable germylene metalloligand. Although several 1:1 Rh and Ir complexes of 4 (5-7) are cleanly formed in solution, all attempts to isolate them in pure form failed due to stability problems. However, crystalline solids of [Mo(κ Ge-4) (CO) ] (8) and [W(κ Ge-4) (CO) ] (9) were isolated and fully characterized by common spectroscopic techniques (8 by X-ray diffraction). DFT calculations were performed on a series of model compounds to elucidate a conceivable interplay between the metal atoms in neutral and cationic bimetallic complexes of the type [Rh(κ E-qE)(CO) Cl] (qE=[Fc(NPh) E] with E=C, Si, Ge). The bonding characteristics of the coordinated Fc-based metalloligands (qE/qE ) are strongly affected upon in silico oxidation of the calculated complexes. The calculated Tolman electronic parameter (TEP) significantly increases by approximately 20 cm (E=C) to 25 cm (E=Si, Ge) upon oxidation. The change in the ligand-donating abilities upon oxidation can mainly be attributed to Coulombic effects, whereas an orbital-based interaction appears to have only a minor influence.