Working at liquid helium temperatures we have obtained velocity spectra for 31 gold complexes. The variations in isomer shift and quadrupole splitting for the series LAuCI. LAuCI, [L = Ph,P, (C6F5) Ph,P, Ph,As, C5H5N, Me,S, and p-tolylisocyanide] ; Ph,PAuX (X = I, Br, CI, N, , OCOMe, CN, and Me) ; and M+AuX,-(X = F, Cl, Br, and I are discussed in terms of sp and dsp2 hybridization of the gold atom. All the quadrupole splitting of the aurous compounds are larger than those of any of the auric compounds.L. D. Roberts and J. 0. Thomson, Phys. Rev., 1963, 129, 664.
The compounds (C6Fs),Ph3,X (X = P, As, or Sb; n = 1, 2, or 3) have been prepared in high yield by an improved method using pentafluorophenyl-lithium. The reactions of these ligands with various rhodium, palladium, and platinum compounds have been investigated and displacement reactions indicate that the complexes L,PtCI, increase in stability in the order of ligands (L). Me,S < (C6Fs),P < (C6F,)Ph2As < (C6F5),PhP < tris(2,6-di-fluorophenyl)phosphine < cyclo-octa-1.5-diene < Ph,As < (C,F,) Ph2P < Ph3P < (PhO),P.The i.r. spectra (400-200 cm.l ) and 19F n.m.r. spectra of the compounds are reported.IN a previous paper we have described rhodium cornplexes of trispentafluorophenylphosphine and the phosphines (C,F,),PhP and (C6F5)Ph2P. Herein we describe rhodium, palladium, and platinum complexes of the phosphines, arsines, and stibines (C6F5)nPh3-nX (n = 1, 2, or 3; X = P, As, or Sb). A summary of the reactions of the ligands, (C,F,),Ph3-,X with some rhodium, palladium, and platinum compounds is given in Table 1. The palladium and platinum complexes isolated are all of the type L,MX, (M = Pd or P t ; X = C1, Br, or I) and since the i.r. spectra (400-200 cm.-l) of the chloride and bromide complexes (Table 2) only exhibit one metal-halogen stretching frequency they presumably have a transconfiguration. The range of frequencies found for these metal-halogen stretching vibrations is in agreement with
Acetato-and trifluoroacetato-triphenylphosphine gold ( I ) have been prepared by reaction of the silver salts with chloro(triphenylphosphine)gold(l). The acetate reacts with the acid HX to form the compounds Ph,PAuX and acetic acid. Reactions with alkyl halides yield alkyl acetates and halogeno(triphenylphosphine)gold(i). Reaction with bromine yields mono-and tri-bromo(triphenylphosphine)gold.
A variety of fluoro-olefins react with RhCI(PPh,), and Rh, CI , L, to give the carbonyl complexes RhCI(CO)L, [L = Ph3P, (C6F&P, (C,F,),PhP, or (C6F5)Ph2P]. It is suggested that the carbon monoxide is formed by the action of small traces of water present in the reactions on fluoro-olefin complexes of the type RhCl(f1uoro-olefin) L, .The action of hydrogen chloride on RhCI(C,F,X) (PPh,), gives the fluoroethyl complexes RhCI,( CFX*CF,H) (PPh,),, (X = H, F, or CI) and it is proposed that this type of rearrangement occurs in some of the hydrolysis reactions of the complexes RhCl(f1uoro-olefin) L, .N.m.r. data on the fluoroethyl complexes are given.WHILE the complex chlorotris(tripheny1phosphine)rhodium(1) reacts with tetrafluoroethylene at room temperature in methylene chloride to form an olefin complex RhCl(C,F,)(PPh3),,1 it was observed that at 120" in benzene both RhCl(PPh,), and Rh,c12[c6F5)3P]4 react with t etrafluoroe thylene to give quantitative yields of the carbonyl complexes trans-RhCl(CO)L, [L = Ph,P or (C,F,),P] . , The formation of carbonylrhodium complexes under such unusual conditions has led us to investigate this reaction further. Under similar conditions te t rafluoroe t hylene and trans-P t HCl (Et,P) , give small yields of a carbonyl cation trams-PtCl(C0) (Et,P), and the complex Rh(acac) (C,F,) (C2H4) catalyses the acetic acid solvolysis of tetrafluoroethylene to give carbon m ~n o x i d e . ~ A variety of fluoro-olefins and phosphine-rhodium( I) complexes react under varying conditions in sealed vessels to give the carbonylrhodium complexes trans-RhCl(CO)L, [L = (
RECENT crystallographic studies have shown that in some phenylphosphine complexes of transition metals there is interaction between an orthohydrogen of the phenyl ring and the metal atom.192 This observation has led us to study metal complexes of trispentafluorophenylphosphine, since the 19F n.m.r. spectra of these compounds might indicate if there is a similar interaction between the ortho-fluorines and the metal.
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