N-Heterocyclic silylenes in coinage metal chemistry: an account of recent advances

Ghosh, Moushakhi; Khan, Shabana

doi:10.1039/d1dt01955d

Cited by 25 publications

(10 citation statements)

References 126 publications

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“… 2 , 3 Recently, we have summarized N -heterocyclic silylene coordinated coinage metal complexes and their potential application in homogeneous catalysis. 4 However, a compilation of the germylene and stannylene coordinated coinage metal complexes remains to be addressed. This motivated us to revisit their existing literature to compile their unique bonding scenario with coinage metals, which demand more investigation.…”

Section: Introductionmentioning

confidence: 99%

“…However, the coinage metal complexes of heavier congeners of carbenes, namely, silylene, germylene, and stannylene, are still in their infancy. They have been mainly used in small-molecule activation, coordination to low valent species, and, nowadays, in homogeneous catalysis. , Recently, we have summarized N -heterocyclic silylene coordinated coinage metal complexes and their potential application in homogeneous catalysis . However, a compilation of the germylene and stannylene coordinated coinage metal complexes remains to be addressed.…”

Section: Introductionmentioning

confidence: 99%

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Coinage Metal Complexes of Germylene and Stannylene

2022

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Group 11 metal (M = Cu, Ag, Au) complexes of heavier tetrylenes (namely, germylene and stannylene) have been studied for several years now. However, the field is mainly unexplored for their potential application either in homogeneous catalysis or in photophysical properties regardless of how the current reports allude to the rich and fascinating chemistry of group 14 elements. In this mini-review, we attempted to summarize the recent advances of heavier tetrylene-stabilized coinage metal complexes, which are majorly dominated by structure elucidation studies. This comprehensive summary intends to help researchers design and fine-tune the tetrylene ligand framework that can lead to coinage metal complexes for future applications as photoemitters in organic light-emitting diode fabrication and efficient catalysts in homogeneous catalysis.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Coinage Metal Complexes of Germylene and Stannylene

2022

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“…Since the pioneering reports on stable silylene–transition metal complexes by Zybill, Tilley, and Ogino, numerous stable silylene complexes have been developed. − Among these, group 11 metal (coinage metal) complexes with silylene ligands have been considered as important species in the process of direct synthesis of chloromethylsilane and catalytic silylene transfer reactions . After the isolation of the silylene–gold complex [(η 5 -Me 5 C 5 )(η 1 -Me 5 C 5 )SiAuCl] by Jutzi et al, some coinage metal complexes coordinated by N-heterocyclic silylene, cyclic dialkylsilylene, amidinato silylene, ,, and silacyclopropylidene were reported. However, the examples of silylene–coinage metal complexes remain limited compared to silylene complexes of transition metals of other groups.…”

Section: Introductionmentioning

confidence: 99%

Silyl(silylene) Coinage Metal Complexes Obtained from Isolable Cyclic Alkylsilylenes

et al. 2022

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A series of coinage metal complexes ligated by cyclic alkylsilylenes (3 M and 4 M ; M = Cu, Ag, Au) were synthesized by the reaction of the corresponding cyclic alkylsilylene, i.e., cyclic dialkylsilylene (CDASi) 1 or cyclic alkylaminosilylene (CAASi) 2 with 0.5 equiv of MCl (M = Cu, Ag) or AuCl-tht (tht = tetrahydrothiophene). The molecular structures of these silylene complexes determined by XRD analysis and the DFT calculations suggested that the silylene–metal bond distances and bond angles around the two-coordinate metal center are dependent on the π acceptor ability and steric demands of the silylene ligands. Complexes 3 Cu and 4 Ag exhibit a fluxional behavior due to the chlorine migration between terminal silicon atoms in solution. The ease of 1,3-Cl migration increases in the order Au < Ag < Cu and 3 < 4. The mechanisms of these migration reactions were investigated by DFT calculations.

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“…The heavier analogue of N-heterocyclic carbene (NHC), namely, N-heterocyclic silylene (NHSi), has attracted significant attention as a strong donor ligand in the last two decades. − The substantial contribution of NHSis was observed in metal-mediated homogeneous catalysis, where they were utilized as ancillary ligands to tune the reactivity of the metal center . In contrast, the use of N-heterocyclic germylene (NHGe) as a spectator ligand in the transition metal-based catalysis is relatively scarce .…”

Section: Introductionmentioning

confidence: 99%

NHSi/NHGe-Supported Copper Halide and Pseudohalide Complexes: Synthesis and Application

et al. 2022

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Herein, we have demonstrated the complexation reaction of silylene and germylene [PhC(NtBu) 2 EN(TMS) 2 ; E = Si (A) and Ge (B)] with several copper(I) salts and further utilized them (1−6) as efficient catalysts in CuAAC reaction. The copper complexes (2 and 4−6) were synthesized from the reaction of [PhC(NtBu) 2 EN(TMS) 2 ] [E = Si (A) or Ge (B)] and CuX (X = Br, I, and SCN). The molecular structures of 2, 4, 5, and 6 were established by single-crystal X-ray diffraction studies. The density functional theory studies indicate that the bimetallic Cu catalyst facilitates the cycloaddition reaction by anchoring the reactants to the close proximity and reducing the energy gap between the frontier orbitals of the dipole and dipolarophile.

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N-Heterocyclic silylenes in coinage metal chemistry: an account of recent advances

Abstract: This feature article intends to highlight and comprehensively summarize the recent developments in the field of silylene-coinage metal chemistry. Recent years have witnessed exponential growth in the utilization of N-heterocyclic...

Cited by 25 publications

References 126 publications

Coinage Metal Complexes of Germylene and Stannylene

Coinage Metal Complexes of Germylene and Stannylene

Silyl(silylene) Coinage Metal Complexes Obtained from Isolable Cyclic Alkylsilylenes

NHSi/NHGe-Supported Copper Halide and Pseudohalide Complexes: Synthesis and Application

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