Rhodium cyclopentadienyl complexes

A. Synthesis of Mononuclear Cyclopentadienyl and Indenyl Rhodium Complexes of OFCOT... 

Cyclopentadienyl cobalt and rhodium complexes with 1,2-benzenedithiolate or S2C2R2 type ligands readily add unsaturated carbon molecules to form tridentate ligands exhibiting S2C donor sets. When nitrenes are added, dithio-lene derived ligands with S2N donor sets result. Scheme 3 shows examples of... 

TABLE I Infrared Carbonyl Stretching Frequencies for Cyclopentadienyl Manganese and Rhodium Complexes"... 

Cyclopentadienyl(triisopropylphosphane)vinylidenerhodium reacted with tellurium in benzene to give a green ethenetellurolato-rhodium complex ... 

Sodium hydrogen telluride and cyclopentadienyl(trimethylphosphane)iodo(iodometh-yl)rhodium(III) produced a dark green tellurolato-rhodium complex. ... 

On treatment with proton sponge 1, cationic rhodium complexes of type 262 have been shown to undergo double intramolecular dehydrofluorinative/C—C coupling to produce quantitatively rhodium complexes of hybrid cyclopentadienyl-phosphine ligands 263 (equation 27)240. 

Two fascinating reports from Hughes and coworkers provide new perspectives on electrophilic attack on saturated fluorocarbons attached to cyclopenta-dienyl rhodium complexes. The first report [68] describes a perplexing observation in which T1(I) salts selectively abstract fluoride from a tertiary C-F bond on a cyclopentadienyl ligand whereas Ag(I) abstracts iodide from the rhodium metal center. 

PO2WC2SH21, Tungsten, dicarbonyl(T) -cyclopentadienyl)hydrido(triphenyl-phosphine)-, 26 98, 28 7 PO3C3H, Trimethyl phosphite, cobalt and rhodium complexes, 28 283, 284 iron complexes, 26 61, 28 171, 29 158 nickel complex, 28 101 P03C,H,5, Triethyl phosphite, iron complexes, 26 61, 28 171, 29 159 nickel complexes, 28 101,104-106 P03C,H2, Isopropyl phosphite, nickel complex, 28 101... 

Aris et al. (9) examined cyclopentadienyl (propene) irondicarbonyl tri-fluoroacetate and dipropenerhodiumacetylacetonate. In the iron complex the olefinic resonances are shifted upheld by approximately 60 ppm (methylene carbon) and approximately 50 ppm (methine carbon). These shifts indicated, in the authors view, that there was extensive backbonding. For the rhodium complex, the methylene and methine resonances are also shifted upheld upon coordination, but the difference between the upheld shifts (J C(l)-d C(2)) is smaller. 

Ferrocene was the first organometallic guest incorporated and numerous spectroscopic and electrochemical studies have been performed on ferrocene, substituted ferrocene, and related metallocene (e.g. cobaltocene) inclusion complexes (444-469]. Half-sandwich cyclopentadienyl- and benzene-metal carbonyl complexes have also been studied quite extensively [470-479] as have // -allyl metal (palladium) complexes [480], diene metal (rhodium) complexes [481-484], acetylene cobalt carbonyl cluster complexes [485], and complexes with metal carbonyls, e.g. Fe(CO)5, Mn2(CO)io, and CoNO(CO)3 [485a]. 

The preparation of two cyclo-octatetraene-gold complexes, (ct)AuCl and (cot)-AU2CI4, has been reported. The structures of biscyclo-octatetraenyl complexes of titanium, vanadium, thallium, and uranium, were deduced from their i.r. spectra. Protonation of (p-cyclo-octatetraene) (p-cyclopentadienyl) complexes has been studied. For the ruthenium and osmium complexes protonation occurs on the eight-membered ring to give CgH moiety co-ordinated to the metal atom via both an T -alkyl and an olefin-metal bond. For the cobalt and rhodium complexes a bicyclic cation (287) is produced which undergoes isomerization to the monocyclic (288). ... 

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