Diphenyl dithiophosphato- and dicyclohexyldithiophosphinato-complexes of rhodium(I)
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 6,p. 541-545
- https://doi.org/10.1039/dt9750000541
Abstract
The reaction of [{Rh(CO)2Cl}2], [Rh(PPh3)3Cl], and [{Rh(cot)Cl}2] with diphenyl dithiophosphate, (PhO)2PS2 –, and dicyclohexyldithiophosphinate, (H11C6)2PS2 –, ions gives neutral four-co-ordinate complexes [RhL2(S–S)] and [Rh(cot)(S–S)][L = CO or PPh3; cot =η-cyclo-octa-1,5-diene; S–S–=(PhO)2PS2 – or (H11C6)2PS2 –]. On treating rhodium(I) dithio-bonded complexes with CO or PPh3 no five-co-ordinate complex has been obtained but only some substitution products of the neutral ligand. 1,2-Bis(diphenylphosphino)ethane and 1,2-bis-(diphenylarsino)ethane, L–L, react, cleaving the metal–sulphur bonds and giving new cationic five-co-ordinate species, [Rh(L–L)2CO](S–S). These easily lose their CO affording cationic [Rh(L–L)2](S–S) and these complexes may also be obtained as tetraphenylborate salts. On bubbling CO through a CH2Cl2 solution containing [Rh(L–L)2](S–S)[S–S–=(H11C6)2PS2 –], neutral [Rh(CO)2(S–S)] is formed. The possibility of identifying the mode of co-ordination of the dithio-ligands by i.r. spectra is briefly discussed. Some oxidative-addition reactions of [Rh(CO)2(S–S)] complexes are also reported: [{Rh(CO)(S–S)X2}2] complexes have been obtained by treating [Rh(CO)2(S–S)] with bromine or iodine, whereas the same reaction with Mel gives [Rh(CO)(COMe)(S–S)l].Keywords
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