5261
fluorine bond. The rhodium compound (CH3)>CjRh(PF& (I, M = Rh) has also been found to undergo a variety of oxidative-addition reactions with iodine compounds of the type R I (R = I, CF3, CkF6,n-C3F7, and n-C7Flj) to give the oxidative-addition products of general structure I11 as listed in Table I. These Table I. Oxidative-Addition Reactions of (CH3)jCjRh(PF3)$0 Yield, Reactant
Product‘]
Color
Deep red Orangebrown MeiCiRh(PF3)(CzF;)I Red-brown C2FJ ir-C3Fit Me;,C,Rh(PF3)(rr-C3Fi)I Deep red /i-CiF121 Me.,CjRh(PFB)(ii-C;FIi)IOrange 12
CF31
MejCeRh(PF3)Iz MejCjRh(PFs)(CF3)l
Mp, “ C Dec >275 Dec >200 230-231 147-149
86-88
95 72
76 77 62
These reactions were all carried out at room temperature in benzene solution using a large excess of the iodine compound. All of these products were characterized by correct anallses for five elements aiid infrared spectra and nmr spectra (proton and fluorine). ti
reactions appear to be the first examples of oxidativeaddition reactions of metal-trifluorophosphine complexes. Similar oxidative-addition reactions have been recently reported for the iridium carbonyl derivative (CH3)jCaIr(CO),. Various metal carbonyl halides also react with Ni(PF,) , in boiling toluene to form metal-trifluorophosphine complexes,I4 sometimes with dehalogenation. Thus Mn(CO)jBr reacts with Ni(PF,), to give a mixture of Mn,(CO)l,-,(PF,), (x = 0, 1, or 2 ) derivatives with removal of the bromine atom. Under appropriate conditions a reasonably pure sample of the known12 compound Mn,(C0)8(PF,)2 could be isolated. Reaction of the rhenium analog Re(CO),Br with excess Ni(PF;OI gives a 2 5 % yield of white Re(CO),(PF,),Br, nip 40-41”, with retention of the bromine atom. Reaction of C:,H,Fe(CO)?I with excess Ni(PF,), gives a 7 7 % yield of brown CjH:,Fe(CO)(PF3)I,mp 102-103”. Reaction of CjHjMo(CO),CI with Ni(PF,), results in dechlorination to give either dark red (CjHJsMo..(CO),PF;, m p 159-160‘ dec, or dark red [CjH2Mo(CO)2PF,],, decomposing at 175”, depending upon the reaction conditions. The nickel compound Ni(PF,), can also be used as a source of trifluorophosphine in reactions with halogenfree metal complexes. Thus, the a-methylmetal deribatibes CH,M(CO),C:H, (M = Mo and w) react with Ni(PF,), in boiling toluene to give the yellow derivatives CH,M(CO),(PF3)CjHj (IV, M = Mo and W). Further details on the compounds described here and closely related ones will be described in future publications.
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( 1 3 ) R . B. Kiiig and A . Efraty, J . Orgorrometal. Chem., 27, 409 (1971). (14) Ne\\ conipouiids prepared i n this \\ark were characterized by cleincntiil aniilyscs. Infrared spectra acid, M hcn obtainable, mnr (protoil a n d fluorine) anti mass spcctra wcrc consistent Mith the proposcd formulatiotir. ( 1 5 ) R . J. Clark, J . P. Hargnden, H . H;r;is, and R . I
