103237-91-8Relevant academic research and scientific papers
Nucleophilic (Michael) Additions to (Ph2P)2C(*)CH2 when chelated to Platinum(II) Dichloride or Di-iodide
Higgins, Simon J.,Shaw, Bernard L.
, p. 1527 - 1530 (2007/10/02)
Treatment of t)2> with (Ph2P)2C(*)CH2 (vdpp) in dichloromethane gave (1a).Treatment of (1a) with a variety of amines or NN-dimethylhydrazine in dichloromethane gave the Michael addition products rapidly and in good yields, viz. .Complex (1a) is more reactive towards Michael addition than is ; thus it forms adducts with H2NC6H4Me-4 or H2NCH2CO2Et, i.e. (7) or (8).It is also remarkably reactive towards carbon nucleophiles, e.g. with 1 equivalent of ethyl acetoacetate or acetylacetone in dichloromethane in the presence of anhydrous sodium carbonate it gave (10) or (11), respectively.On prolonged treatment of (1a) with sodium iodide in acetone, acetone added to the vinylidene double bond to give (13a).The di-iodo-complex (1b) was prepared by treating (1a) with NBun4I in dichloromethane.Complex (1b) reacted with Me2NNH2 or amine to give adducts, e.g. (2b) or (5b), but not with carbon nucleophiles under conditions when the corresponding dichloro-complex (1a) underwent Michael addition.Variable-temperature n.m.r. spectroscopy was used to compare the rates of some of these reactions; 31P-(1H), 1H-(31P), and 1H n.m.r. and i.r. data are given.
The Very High Activity of (Ph2P)2C=CH2 to Michael Additions when complexed to Platinum(II) or Platinum(IV)
Fontaine, Xavier L. R.,Hassan, Fatma S. M.,Higgins, Simon J.,Jacobsen, Grant B.,Shaw, Bernard L.,Thornton-Pett, Mark
, p. 1635 - 1636 (2007/10/02)
Complexes of the types , , or undergo Michael additions with various amines, hydrazines, or carbon nucleophiles (ethyl acetoacetate or acetone) to the vinylidene double bond; i
