金属磷酸烯烯的可逆脱羰反应。

IF 3.9 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - A European Journal Pub Date : 2025-05-15 DOI:10.1002/chem.202501527

Matthew J Reveley, Joey Feld, Jose M Goicoechea

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引用次数: 0

摘要

用已知的钴(I)磷烯配合物Co(DippPDI)(PCO) (DippPDI = 1,1′-（吡啶-2,6-二基）二（N-（2,6-二异丙基苯基）乙二亚胺）与Sn[CH(SiMe3)2]2反应合成了金属化磷烯。所得化合物Co(DippPDI)(Co){P=Sn[CH(SiMe3)2]2}含有一个定域的P=Sn双键，但其反应方式类似于磷酸烯转移试剂，表明Co(DippPDI)(Co){P=Sn[CH(SiMe3)2]2}似乎与Co(DippPDI)（PCO）和Sn[CH(SiMe3)2]2处于平衡状态。这是由于在与Sn[CH(SiMe3)2]2脱羰基化时，从磷酸烯烯前体Co(DippPDI)（PCO）中挤出的一氧化碳留在钴的配位球中。新型磷酸烯化合物（IDipp）Au(PCO) （IDipp = 1,3-二（2,6-二异丙基苯基）咪唑-2-酰基）和（DippNacNac）Zn(PCO) (DippNacNac = HC[C(Me)N(Dipp)]2；Dipp = 2,6- ipr2c6h3)可由Co(DippPDI)(Co){P=Sn[CH(SiMe3)2]2}与Au(IDipp)Cl或（DippNacNac）ZnCl·LiCl(OEt2)2反应合成。在前者的情况下，释放的锡炔Sn[CH(SiMe3)2]2最终插入Au-PCO键，形成锡（IV）配合物（IDipp）AuSn(PCO)[CH(SiMe3)2]2。

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Reversible Decarbonylation of a Metal Phosphaketene.

The synthesis of a metalated phosphastannene by reaction of the known cobalt(I) phosphaketene complex Co(^DippPDI)(PCO) (^DippPDI = 1,1'-(pyridine-2,6-diyl)bis(N-(2,6-diisopropylphenyl)ethan-1-imine) with Sn[CH(SiMe₃)₂]₂ is described. The resulting compound, Co(^DippPDI)(CO){P═Sn[CH(SiMe₃)₂]₂}, contains a localized P═Sn double bond, yet reacts like a phosphaketene transfer reagent, suggesting that, in solution, Co(^DippPDI)(CO){P═Sn[CH(SiMe₃)₂]₂} appears to exist in equilibrium with Co(^DippPDI)(PCO) and Sn[CH(SiMe₃)₂]₂. This is facilitated by the fact that, on decarbonylation with Sn[CH(SiMe₃)₂]₂, the carbon monoxide extruded from the phosphaketene precursor Co(^DippPDI)(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 (^DippNacNac)Zn(PCO) (^DippNacnac = HC[C(Me)N(Dipp)]₂; Dipp = 2,6-ⁱPr₂C₆H₃) can be synthesized by reaction of Co(^DippPDI)(CO){P═Sn[CH(SiMe₃)₂]₂} with Au(IDipp)Cl or (^DippNacNac)ZnCl·LiCl(OEt₂)₂, respectively. In the case of the former, the released stannylene Sn[CH(SiMe₃)₂]₂ ultimately inserts into the Au─PCO bond, affording the tin(IV) complex (IDipp)AuSn(PCO)[CH(SiMe₃)₂]₂.

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来源期刊

Chemistry - A European Journal 化学-化学综合

CiteScore

7.90

自引率

4.70%

发文量

1808

审稿时长

1.8 months

期刊介绍： Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields. Based in Europe Chemistry—A European Journal provides an excellent platform for increasing the visibility of European chemistry as well as for featuring the best research from authors from around the world. All manuscripts are peer-reviewed, and electronic processing ensures accurate reproduction of text and data, plus short publication times. The Concepts section provides nonspecialist readers with a useful conceptual guide to unfamiliar areas and experts with new angles on familiar problems. Chemistry—A European Journal is published on behalf of ChemPubSoc Europe, a group of 16 national chemical societies from within Europe, and supported by the Asian Chemical Editorial Societies. The ChemPubSoc Europe family comprises: Angewandte Chemie, Chemistry—A European Journal, European Journal of Organic Chemistry, European Journal of Inorganic Chemistry, ChemPhysChem, ChemBioChem, ChemMedChem, ChemCatChem, ChemSusChem, ChemPlusChem, ChemElectroChem, and ChemistryOpen.