P–Ge/Sn π Interactions Versus Arene···Ge/Sn Contacts for the Stabilization of Diphosphatetrylenes, (R<sub>2</sub>P)<sub>2</sub>E (E = Ge, Sn)

A stable O,N‐heterocyclic stannylene 1 bearing novel tetradentate 2,4‐di‐tert‐butyl‐6‐((2‐(1‐((pyridin‐2‐ylmethyl)imino)ethyl)phenyl)amino)phenolate ligand (RAPH2) was synthesized and characterized. Complex 1 is monomeric in crystal and solution due to two additional intramolecular N → Sn donor–acceptor interactions. The diverse reactivity of compound 1 towards various iron carbonyl compounds was studied. Oxidative addition of [Fe2(μ‐S2)(CO)6]2 to the tin center of 1 resulted in a new six‐coordinate Sn(IV) compound 2 containing two Sn–S bonds. The reaction of 1 with Fe2(CO)9 led to the formation of a stable tin(II) adduct 3 – RAPSn‐Fe(CO)4. The interaction between 1 and [(η5‐C5H5)Fe(CO)2]2 resulted in a transformation of the ligand skeleton. During this reaction, the tin center is oxidized to the tetravalent state, and the donor ═N–CH2–Py group is converted into an anionic one with the loss of the methylene hydrogen atom. The molecular structures of all obtained compounds were determined by single‐crystal X‐ray diffraction. The novel stannylene 1 demonstrates striking activity in benzaldehydes' hydroboration reactions down to 0.02 mole percent of the catalyst loading under mild conditions.

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“…This situation is well‐known to stabilize low‐valent group 14 element compounds. [ 17 ] The Sn … R orange distances are 3.8368(5) Å.…”

Section: Resultsmentioning

confidence: 99%

Stable heterocyclic stannylene: The metal, ligand‐centered reactivity, and effective catalytic hydroboration of aldehydes

Arsenyeva

Klimashevskaya

Pashanova

et al. 2022

Applied Organom Chemis

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Isolation of an Anionic Dicarbene Embedded Sn₂P₂ Cluster and Reversible CO₂ Uptake

Ebeler,

Vishnevskiy,

Neumann

et al. 2023

Advanced Science

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Decarbonylation of a cyclic bis‐phosphaethynolatostannylene [(ADC)Sn(PCO)]2 based on an anionic dicarbene framework (ADC = PhC{N(Dipp)C}2; Dipp = 2,6‐iPr2C6H3) under UV light results in the formation of a Sn2P2 cluster compound [(ADC)SnP]2 as a green crystalline solid. The electronic structure of [(ADC)SnP]2 is analyzed by quantum‐chemical calculations. At room temperature, [(ADC)SnP]2 reversibly binds with CO2 and forms [(ADC)2{SnOC(O)P}SnP]. [(ADC)SnP]2 enables catalytic hydroboration of CO2 and reacts with elemental selenium and Fe2(CO)9 to afford [(ADC)2{Sn(Se)P2}SnSe] and [(ADC)Sn{Fe(CO)4}P]2, respectively. All compounds are characterized by multinuclear NMR spectroscopy and their solid‐state molecular structures are determined by single‐crystal X‐ray diffraction.

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Spontaneous Decomposition of an Extraordinarily Twisted and Trans‐Bent Fully‐Phosphanyl‐Substituted Digermene to an Unusual Ge^I Cluster

et al. 2022

Self Cite

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Ditetrelenes R 2 E=ER 2 (E = Si, Ge, Sn, Pb) substituted by multiple N/P/O/S-donor groups are extremely rare due to their propensity to disaggregate into their tetrylene monomers R 2 E. We report the synthesis of the first fully phosphanyl-substituted digermene {(Mes) 2 P} 2 Ge=Ge{P(Mes) 2 } 2 (3, Mes = 2,4,6-Me 3 C 6 H 2 ), which adopts a highly unusual structure in the solid state, that is both strongly trans-bent and highly twisted. Variable-temperature 31 P{ 1 H} NMR spectroscopy suggests that 3 persists in solution, but is subject to a dynamic equilibrium between two conformations, which have different geometries about the Ge=Ge bond (twisted/non-twisted) due to a difference in the nature of their π-stacking interactions. Compound 3 undergoes unprecedented, spontaneous decomposition in solution to give a unique Ge I cluster {(Mes) 2 P} 4 Ge 4 •5 CyMe (7).

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P–Ge/Sn π Interactions Versus Arene···Ge/Sn Contacts for the Stabilization of Diphosphatetrylenes, (R₂P)₂E (E = Ge, Sn)

Cited by 9 publications

References 56 publications

Stable heterocyclic stannylene: The metal, ligand‐centered reactivity, and effective catalytic hydroboration of aldehydes

Stable heterocyclic stannylene: The metal, ligand‐centered reactivity, and effective catalytic hydroboration of aldehydes

Isolation of an Anionic Dicarbene Embedded Sn₂P₂ Cluster and Reversible CO₂ Uptake

Spontaneous Decomposition of an Extraordinarily Twisted and Trans‐Bent Fully‐Phosphanyl‐Substituted Digermene to an Unusual Ge^I Cluster

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P–Ge/Sn π Interactions Versus Arene···Ge/Sn Contacts for the Stabilization of Diphosphatetrylenes, (R2P)2E (E = Ge, Sn)

Cited by 9 publications

References 56 publications

Stable heterocyclic stannylene: The metal, ligand‐centered reactivity, and effective catalytic hydroboration of aldehydes

Stable heterocyclic stannylene: The metal, ligand‐centered reactivity, and effective catalytic hydroboration of aldehydes

Isolation of an Anionic Dicarbene Embedded Sn2P2 Cluster and Reversible CO2 Uptake

Spontaneous Decomposition of an Extraordinarily Twisted and Trans‐Bent Fully‐Phosphanyl‐Substituted Digermene to an Unusual GeI Cluster

Contact Info

Product

Resources

About

P–Ge/Sn π Interactions Versus Arene···Ge/Sn Contacts for the Stabilization of Diphosphatetrylenes, (R₂P)₂E (E = Ge, Sn)

Isolation of an Anionic Dicarbene Embedded Sn₂P₂ Cluster and Reversible CO₂ Uptake

Spontaneous Decomposition of an Extraordinarily Twisted and Trans‐Bent Fully‐Phosphanyl‐Substituted Digermene to an Unusual Ge^I Cluster