金属磷杂乙酮烯的可逆脱羰反应

Reversible Decarbonylation of a Metal Phosphaketene.

作者信息

Reveley Matthew J, Feld Joey, Goicoechea Jose M

机构信息

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Rd., Oxford, OX1 3TA, UK.

Department of Chemistry, Indiana University, 800 East Kirkwood Ave., Bloomington, IN, 47405, USA.

出版信息

Chemistry. 2025 Jun 26;31(36):e202501527. doi: 10.1002/chem.202501527. Epub 2025 May 24.

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

描述了通过已知的钴（I）磷杂环丁二烯配合物Co（PDI）（PCO）（PDI = 1,1'-（吡啶-2,6-二基）双（N-（2,6-二异丙基苯基）乙-1-亚胺）与Sn[CH（SiMe）]反应合成金属化磷锡烯的过程。所得化合物Co（PDI）（CO）{P═Sn[CH（SiMe）]}含有一个局域化的P═Sn双键，但表现得像磷杂环丁二烯转移试剂，这表明在溶液中，Co（PDI）（CO）{P═Sn[CH（SiMe）]}似乎与Co（PDI）（PCO）和Sn[CH（SiMe）]处于平衡状态。这一过程因以下事实而变得容易：在用Sn[CH（SiMe）]进行脱羰基反应时，从磷杂环丁二烯前体Co（PDI）（PCO）挤出的一氧化碳仍保留在钴的配位球中。新型磷杂环丁二烯化合物（IDipp）Au（PCO）（IDipp = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚基）和（NacNac）Zn（PCO）（Nacnac = HC[C（Me）N（Dipp）]；Dipp = 2,6-PrCH）可分别通过Co（PDI）（CO）{P═Sn[CH（SiMe）]}与Au（IDipp）Cl或（NacNac）ZnCl·LiCl（OEt）反应合成。对于前者，释放出的亚锡烯Sn[CH（SiMe）]最终插入Au─PCO键中，得到锡（IV）配合物（IDipp）AuSn（PCO）[CH（SiMe）]。