Fully Tin‐Coated Coinage Metal Ions: A Pincer‐Type Bis‐stannylene Ligand for Exclusive Tetrahedral Complexation

Krätschmer, Frederic; Sun, Xiaofei; Gillhuber, Sebastian; Kucher, Hannes; Franzke, Yannick J.; Weigend, Florian; Roesky, Peter W.

doi:10.1002/chem.202203583

Cited by 10 publications

(19 citation statements)

References 80 publications

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“…188 This compound features a large coupling constant previously studied experimentally and computationally with the two-component mSNSO−DLU-X2C ansatz. 188 Here, the results are complemented with the SR DLU-X2C and the nonrelativistic approach. For the first, the x2c-TZVPall (auxiliary) basis sets 136 are applied.…”

Section: Methodsmentioning

confidence: 94%

“…is used for the norm of the CPKS residuum. Computational studies are carried out with the BH&HLYP, ,, PBE0, , TPSSh, , ωB97X-D, and TMHF functionals using large grids (grid size 3a). − Structures are taken from ref . All calculations use the multipole-accelerated RI- J (MARI- J ) approximation and snK for the CPKS part.…”

Section: Methodsmentioning

confidence: 99%

“…Fourth, the 1 J ( 119 Sn, 117 Sn) coupling constant of the novel pincer-type bis-stannylene ligand SnNSn is studied . This compound features a large coupling constant previously studied experimentally and computationally with the two-component mSNSO–DLU-X2C ansatz . Here, the results are complemented with the SR DLU-X2C and the nonrelativistic approach.…”

Section: Methodsmentioning

confidence: 99%

“…The novel pincer-type bis-stannylene ligand SnNSn, depicted in Figure 2, recently allowed us to synthesize and study coinage metal complexes with Cu(I), Ag(I), and Au(I). 188 Here, the coinage metals are stabilized in exclusively tetrahedral coordination geometries. The pincer ligand itself shows a very large 1 J( 119 Sn, 117 Sn) coupling constant of 4087 Hz.…”

Section: Tin Pincer Ligand and Sn−sn Coupling Constantmentioning

confidence: 99%

“…Molecular structure of the pincer-type bis-stannylene ligand SnNSn . The compound consists of 107 atoms and was synthesized in ref . Color code: H white, C gray, N purple, and Sn pink.…”

Section: Assessment Of Accuracy and Efficiencymentioning

confidence: 99%

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Reducing Exact Two-Component Theory for NMR Couplings to a One-Component Approach: Efficiency and Accuracy

Franzke

2023

J. Chem. Theory Comput.

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The self-consistent and complex spin–orbit exact two-component (X2C) formalism for NMR spin–spin coupling constants [J. Chem. Theory Comput.20211738743994] is reduced to a scalar one-component ansatz. This way, the first-order response term can be partitioned into the Fermi-contact (FC) and spin–dipole (SD) interactions as well as the paramagnetic spin–orbit (PSO) contribution. The FC+SD terms are real and symmetric, while the PSO term is purely imaginary and antisymmetric. The relativistic one-component approach is combined with a modern density functional treatment up to local hybrid functionals including the response of the current density. Computational demands are reduced by factors of 8–24 as shown for a large tin compound consisting of 137 atoms. Limitations of the current ansatz are critically assessed for Sn, Pb, Pd, and Pt compounds, i.e. the one-component treatment is not sufficient for tin compounds featuring a few heavy halogen atoms.

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Section: Methodsmentioning

confidence: 94%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Tin Pincer Ligand and Sn−sn Coupling Constantmentioning

confidence: 99%

“…Molecular structure of the pincer-type bis-stannylene ligand SnNSn . The compound consists of 107 atoms and was synthesized in ref . Color code: H white, C gray, N purple, and Sn pink.…”

Section: Assessment Of Accuracy and Efficiencymentioning

confidence: 99%

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Reducing Exact Two-Component Theory for NMR Couplings to a One-Component Approach: Efficiency and Accuracy

Franzke

2023

J. Chem. Theory Comput.

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Polydentate Amidinato‐Silylenes, ‐Germylenes and ‐Stannylenes

Cabeza,

García‐Álvarez

2024

Chemistry A European J

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This review article focuses on amidinatotetrylenes that potentially can (or have already shown to) behave as bi‐ or tridentate ligands because they contain at least one amidinatotetrylene moiety (silylene, germylene or stannylene) and one (or more) additional coordinable fragment(s). Currently, they are being widely used as ligands in coordination chemistry, small molecule activation and catalysis. This review classifies those that have been isolated as transition metal‐free compounds into five families that differ in the position(s) of the donor group(s) (D) on the amidinatotetrylene moiety, namely: ED{R1NC(R2)NR1}, EX{DNC(R2)NR1}, EX{R1NC(D)NR1}, EX{DNC(R2)ND} and E{R1NC(R2)ND}2 (E = Si, Ge or Sn). Those that do not exist as transition metal‐free compounds but have been observed as ligands in transition metal complexes are cyclometallated and ring‐opened amidinatotetrylene ligands. This article presents schematic descriptions of their structures, the approaches used for their syntheses and a quick overview of their involvement (as ligands) in transition metal‐catalysed reactions. The literature is covered up to the end of 2023.

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Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

Alonso,

Cabeza,

García-Álvarez

et al. 2024

Inorg. Chem.

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E(hmds)(bqfam) (E = Ge (1a), Sn (1b); hmds = N(SiMe3)2, bqfam = N,N′-bis(quinol-8-yl)formamidinate), which are amidinatotetrylenes equipped with quinol-8-yl fragments on the amidinate N atoms, have been synthesized from the formamidine Hbqfam and Ge(hmds)2 or SnCl(hmds). Both 1a and 1b are fluxional in solution at room temperature, as the E atom oscillates from being attached to the two amidinate N atoms to being chelated by an amidinate N atom and its closest quinolyl N atom (both situations are similarly stable according to density functional theory calculations). The hmds group of 1a and 1b is still reactive and the deprotonation of another equivalent of Hbqfam can be achieved, allowing the formation of the homoleptic derivatives E(bqfam)2 (E = Ge, Sn). The reactions of 1a and 1b with [AuCl(tht)] (tht = tetrahydrothiophene), [PdCl2(MeCN)2], [PtCl2(cod)] (cod = cycloocta-1,5-diene), [Ru3(CO)12] and [Co2(CO)8] have been investigated. The gold(I) complexes [AuCl{κE-E(hmds)(bqfam)}] (E = Ge, Sn) have a monodentate κE-tetrylene ligand and display fluxional behavior in solution the same as that of 1a and 1b. However, the palladium(II) and platinum(II) complexes [MCl{κ3 E,N,N′ -ECl(hmds)(bqfam)}] (M = Pd, Pt; E = Ge, Sn) contain a κ3 E,N,N′-chloridotetryl ligand that arises from the insertion of the tetrylene E atom into an M–Cl bond and the coordination of an amidinate N atom and its closest quinolyl N atom to the metal center. Finally, the binuclear ruthenium(0) and cobalt(0) complexes [Ru2{μE-κ3 E,N,N′ -E(hmds)(bqfam)}(CO)6] and [Co2{μE-κ3 E,N,N′ -E(hmds)(bqfam)}(μ-CO)(CO)4] (E = Ge, Sn) have a related κ3 E,N,N′ -tetrylene ligand that bridges two metal atoms through the E atom. For the κ3 E,N,N′-metal complexes, the quinolyl fragment not attached to the metal is pendant in all the germanium compounds but, for the tin derivatives, is attached to (in the Pd and Pt complexes) or may interact with (in the Ru2 and Co2 complexes) the tin atom.

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Fully Tin‐Coated Coinage Metal Ions: A Pincer‐Type Bis‐stannylene Ligand for Exclusive Tetrahedral Complexation

Cited by 10 publications

References 80 publications

Reducing Exact Two-Component Theory for NMR Couplings to a One-Component Approach: Efficiency and Accuracy

Reducing Exact Two-Component Theory for NMR Couplings to a One-Component Approach: Efficiency and Accuracy

Polydentate Amidinato‐Silylenes, ‐Germylenes and ‐Stannylenes

Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

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