4.5 Article

Synthesis and reactivity of [M(η3-allyl)(η2-amidinato) (CO)2(phosphonium ylide)] (M = Mo, W): Investigation of the ligand properties of phosphonium ylides

期刊

INORGANICA CHIMICA ACTA
卷 471, 期 -, 页码 310-315

出版社

ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2017.11.019

关键词

Phosphonium ylide; Electron donating ability; Bond strength; DFT calculations

资金

  1. JSPS KAKENHI [JP17K05805]
  2. Collaborative Research Program of Institute for Chemical Research, Kyoto University [2017-20]
  3. Grants-in-Aid for Scientific Research [17K05805] Funding Source: KAKEN

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Phosphonium ylide complexes of Mo and W formulated as [M(eta(3)-allyl){eta(2)-(NPh)(2)CH}(CO)(2)(CH2PR3)] (M = Mo, R = Me: 2a-Mo; M = Mo, R = Ph: 2b-Mo, and M = W, R = Me: 2a-W) were prepared by the reaction of amidinato(pyridine) complex, [M(eta(3)-allyl){eta(2)-(NPh)(2)CH}(CO)(2)(NC5H5)] (M = Mo: 1-Mo and M = W: 1-W), with a phosphonium ylide, CH2PR3 (R = Me, Ph), which was generated in situ by the reaction of the corresponding phosphonium salt with (BuLi)-Bu-n. These complexes were characterized spectroscopically, as well as by the X-ray diffraction. The phosphonium ylide ligand shows stronger electron donating ability toward the metal than N-heterocyclic carbene or phosphine ligands. This trend is supported by the comparison of the spectroscopic data and the DFT calculations. We also investigated the reactivity of the phosphonium ylide complexes 2-Mo with two-electron donors such as PEt3 and NHC. In the case of the PPh3 ylide complex (2b-Mo), the substitution reaction of the ylide ligand for the two-electron donors took place cleanly to yield the corresponding complexes. On the other hand, in the PMe3 ylide complex (2a-Mo), the substituted complexes formed but the unreacted ylide complex 2a-Mo was also present in the reaction mixture. These results show that the bond strength of the M-C(phosphonium ylide) bond is affected by the substituents on the phosphorus atom. (C) 2017 Elsevier B.V. All rights reserved.

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