Coinage Metal Complexes of Germylene and Stannylene

2023

Inorg. Chem.

We show that a tris(carbene)borate (TCB) ligand, namely [PhB( t BuIm) 3 ] − ([PhB( t BuIm) 3 ] − = phenyltris(3-tert-butylimidazol-2-ylidene)borato), is capable of stabilizing an unprecedented nucleophilic Sn(II) cation salt. Unlike known Sn(II) cations, the strong electron-donating ability of [PhB-( t BuIm) 3 ] − makes the cationic tin atom electron-rich, σ-donating yet slightly πaccepting, which allows for the ensuing facile oxidation with o-chloranil and S 8 as well as coordination with coinage metals. The former oxidations give the Sn(IV) cation salts, while the latter reactions produce the metal complexes. The electronic structures of these species are thoroughly probed by quantum chemical computations. These results uncover an added role for TCB ligands in isolating unprecedented p-block species.

Section: Resultsmentioning

confidence: 99%

Utilization of a Tris(carbene)borate Ligand for Umpolung Reactivity of a Nucleophilic Tin(II) Cation Salt

2023

Inorg. Chem.

“…Whereas numerous TM stannylene complexes have been documented, 97 coinage metal complexes ligated with a Sn(II) cation are hitherto unknown. We thus examined the nucleophilic behavior of Sn(1) in 2[OTf] towards coinage metals (Scheme 3).…”

Section: Coordination Behavior Toward Coinage Metalsmentioning

confidence: 99%

A Nucleophilic Tin(II) Cation Salt

2022

Preprint

We show that one of the tris(carbene)borate (TCB) ligands, namely PhB(tBuIm)3 (PhB(tBuIm)3 = phenyltris(3-tert-butylimidazol-2-ylidene)borato), is capable of stabilizing an unprecedented nucleophilic Sn(II) cation salt. Unlike known Sn(II) cations, the strong electron-donating ability of PhB(tBuIm)3 makes the cationic tin atom electron-rich, σ-donating yet slightly π-accepting, which allows for the ensuing facile oxidation with o-chloranil and S8 as well as coordination with coinage metals. The former oxidations give rare Sn(IV) cation salts, while the latter reactions produce novel metal complexes. The electronic structures of these species are thoroughly probed by quantum chemical computations. These results unravel an added role for TCB ligands in isolating unprecedented p-block species.

“…Whereas numerous TM stannylene complexes have been documented, 25 coinage metal complexes ligated with a Sn(II) cation are hitherto unknown. We thus examined the nucleophilic behavior of Sn(1) in 2[OTf] towards coinage metals (Scheme 3).…”

Section: Coordination Behavior Toward Coinage Metalsmentioning

confidence: 99%

A Nucleophilic Tin(II) Cation Salt

2022

Preprint

We show that one of the tris(carbene)borate (TCB) ligands, namely [PhB(tBuIm)3]- ([PhB(tBuIm)3]- = phenyltris(3-tert-butylimidazol-2-ylidene)borato), is capable of stabilizing an unprecedented nucleophilic Sn(II) cation salt. Unlike known Sn(II) cations, the strong electron-donating ability of [PhB(tBuIm)3]- makes the cationic tin atom electron-rich, σ-donating yet slightly π-accepting, which allows for the ensuing facile oxidation with o-chloranil and S8 as well as coordination with coinage metals. The former oxidations give rare Sn(IV) cation salts, while the latter reactions produce novel metal complexes. The electronic structures of these species are thoroughly probed by quantum chemical computations. These results unravel an added role for TCB ligands in isolating unprecedented p-block species.