Reversible Decarbonylation of a Metal Phosphaketene

The synthesis of a metalated phosphastannene by reaction of the known cobalt(I) phosphaketene complex Co(<sup>Dipp</sup>PDI)(PCO) (<sup>Dipp</sup>PDI = 1,1'-(pyridine-2,6-diyl)bis(N-(2,6-diisopropylphenyl)ethan-1-imine) with Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> is described. The resulting compound, Co(<sup>Dipp</sup>PDI)(CO){P═Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>}, contains a localized P═Sn double bond, yet reacts like a phosphaketene transfer reagent, suggesting that, in solution, Co(<sup>Dipp</sup>PDI)(CO){P═Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>} appears to exist in equilibrium with Co(<sup>Dipp</sup>PDI)(PCO) and Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>. This is facilitated by the fact that, on decarbonylation with Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>, the carbon monoxide extruded from the phosphaketene precursor Co(<sup>Dipp</sup>PDI)(PCO) remains in the coordination sphere of cobalt. The novel phosphaketene compounds (IDipp)Au(PCO) (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and (<sup>Dipp</sup>NacNac)Zn(PCO) (<sup>Dipp</sup>Nacnac = HC[C(Me)N(Dipp)]<sub>2</sub>; Dipp = 2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) can be synthesized by reaction of Co(<sup>Dipp</sup>PDI)(CO){P═Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>} with Au(IDipp)Cl or (<sup>Dipp</sup>NacNac)ZnCl·LiCl(OEt<sub>2</sub>)<sub>2</sub>, respectively. In the case of the former, the released stannylene Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> ultimately inserts into the Au─PCO bond, affording the tin(IV) complex (IDipp)AuSn(PCO)[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>.

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Publication Details

Journal
Chemistry - A European Journal
Published
2025-05-15
DOI
https://doi.org/10.1002/chem.202501527
Citations
1
Primary Topic
Synthesis and characterization of novel inorganic/organometallic compounds
Type
article
Field-Weighted Citation Impact
0.54

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article

Reversible Decarbonylation of a Metal Phosphaketene

Joey Feld, José M. Goicoechea, Matthew J. Reveley
1 citations
Chemistry - A European Journal
Synthesis and characterization of novel inorganic/organometallic compounds
0.54
article

Reversible Decarbonylation of a Metal Phosphaketene

Joey Feld, José M. Goicoechea, Matthew J. Reveley
article en
1 citations

Abstract

The synthesis of a metalated phosphastannene by reaction of the known cobalt(I) phosphaketene complex Co(<sup>Dipp</sup>PDI)(PCO) (<sup>Dipp</sup>PDI = 1,1'-(pyridine-2,6-diyl)bis(N-(2,6-diisopropylphenyl)ethan-1-imine) with Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> is described. The resulting compound, Co(<sup>Dipp</sup>PDI)(CO){P═Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>}, contains a localized P═Sn double bond, yet reacts like a phosphaketene transfer reagent, suggesting that, in solution, Co(<sup>Dipp</sup>PDI)(CO){P═Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>} appears to exist in equilibrium with Co(<sup>Dipp</sup>PDI)(PCO) and Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>. This is facilitated by the fact that, on decarbonylation with Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>, the carbon monoxide extruded from the phosphaketene precursor Co(<sup>Dipp</sup>PDI)(PCO) remains in the coordination sphere of cobalt. The novel phosphaketene compounds (IDipp)Au(PCO) (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and (<sup>Dipp</sup>NacNac)Zn(PCO) (<sup>Dipp</sup>Nacnac = HC[C(Me)N(Dipp)]<sub>2</sub>; Dipp = 2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) can be synthesized by reaction of Co(<sup>Dipp</sup>PDI)(CO){P═Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>} with Au(IDipp)Cl or (<sup>Dipp</sup>NacNac)ZnCl·LiCl(OEt<sub>2</sub>)<sub>2</sub>, respectively. In the case of the former, the released stannylene Sn[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> ultimately inserts into the Au─PCO bond, affording the tin(IV) complex (IDipp)AuSn(PCO)[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>.

Chemistry - A European JournalVol. 31(36)
Mansfield University (US), Oxford Research Group (GB), University of Oxford (GB), Indiana University Bloomington (US)
University of Oxford
Clean water and sanitation
Openalex Percentile: Top 36%
Synthesis and characterization of novel inorganic/organometallic compounds
0.54
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Reversible Decarbonylation of a Metal Phosphaketene — Joey Feld, José M. Goicoechea, et al. · Chemistry - A European Journal (2025) | TGRS Research Map | TGRS