Dimethylphenylphosphine

Where X is phenyl, the result of irradiation (sunlight, mercury lamp) is the formation of Ru(NO)X3(PPh3)(OPPh3) (X = Cl, Br) in the case of the diethyl-phenylphosphine complex, irradiation causes isomerization to the cis,mer-isomer. The frans,mer-isomer is the usual synthetic product, but in the case of dimethylphenylphosphine the/ac-isomer was obtained using short reaction times it isomerized to the usual mer,trans-isomer on heating [123],... 

Other halides can be introduced by metathesis. Figure 2.55 summarizes some of the complexes isolable with dimethylphenylphosphine, similar in general to the corresponding iridium complexes (section 2.13.3), including the photochemical isomerization of the mer-isomer. 

Figure 2.91 Structural data for iridium(III) complexes of dimethylphenylphosphine.

Figure 2.92 Reactions of iridium(III) dimethylphenylphosphine trihydro and trimethyl...

Trimethylphosphine and dimethylphenylphosphine form crystalline adducts (61) with chlorodiphenylphosphine. The adducts are in equilibrium with their starting materials in dichloromethane. 

Two papers have appeared on the reactions of halogenophosphines with tervalent phosphorus compounds. In a detailed study of the reactions at 20 °C of a range of tertiary phosphines with phosphorus trichloride, dichlorophenylphosphine, and chlorodiphenylphosphine, it has been shown that, in general, 1 1 adducts are formed, provided that the tertiary phosphine is a good nucleophile. With diphenylchlorophosphine, for example, an adduct (18) is formed with dimethylphenylphosphine, but not with diphenylmethylphosphine, although the relative importance of steric and electronic factors remains to be established. The related reactions of phosphorus trichloride and of dichlorophenylphosphine are much more complex, and the initial crystalline products are not amenable to analysis. The reactions at 280 °C of a similar system have been shown to lead to halogen exchange, e.g. the conversion of (19) to (20). 

Kariis, H., Westermark, G., Persson, I. and Liedberg, B. (1998) Infrared Spectroscopic and Temperature-Programmed Desorption Studies of Dimethylphenylphosphine Adsorbed on the Coinage Metals. Langmuir, 14, 2736-2743. 

Tetrahydrofuranylidene(dimethylphenylphosphine-trimethyl-phosphine)-2,4,6-trimethylphenylnickel perchlorate... 

Tetrahydropyranylidene-bis(dimethylphenylphosphine)-3,4,6-trimethyl-phenyl-nickel perchlorate, 3877... 

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