Abstract
The syntheses of C5H5Co(CN-t-Bu)I2 (2) and C5H5Co(CNPh)I2 (3) are reported. On reaction with PMe3, CNR′ and CH3CN, these complexes (as well as C5H5Co(CNMe)I2 (1)) are converted to the cationic species [C5H5CoI(CNR)PMe3]+, [C5H5Co(CNR)(PMe3)2]2+, [C5H5Co(CNR)-(CNR′)PMe3]2+, and [C5H5Co (CNR)(CH3CN)PMe3]2+, which are isolated as the PF6 salts (4 − 13). The corresponding carbonyl compounds [C5H5Co (CO)(CNR)PMe3]2+ can also be prepared but due to the lability of the CO group, analytically pure samples of the PF6 salts could not be isolated. Reduction of [C5H5CoI(CNR)PMe3]PF6 with sodium amalgam provides a new route to the uncharged complexes C5H5Co(CNR)PMe3 (15 − 17). The preparation of the bis(isocyanide)cobalt(I) compound C5H5Co(CNMe)2 (18) has similarly been achieved.

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