| Abstract | The reaction of K[Co(CO)4] and PCl2(TMP) at –5°C leads to the unstable and reactive -phosphinidene complex [Co2(CO)6{-P(TMP)}] (1), while the same reaction carried out at 35°C gives the chlorophosphido and phosphinidene bridged cluster [Co3(CO)7{-P(Cl)TMP}{ 3-P(TMP)}] (2) (TMP=2,2,6,6-tetramethylpiperidyl). Compound 1 reacts with dppm (dppm=bis(diphenyl- phosphino)methane) and [Co2(CO)8] to form the more stable substitution product [Co2(CO)4{-P(TMP)}(-dppm)] (3) and [Co4(CO)7(-CO)3{ 3-P(TMP)}] (4) respectively. The first example of a cationic 3-phosphinidene cluster compound [Co3(CO)9{ 3-P(TMP)}][AlCl4] (5) is obtained from reaction of 3 with AlCl3. The X-ray structures of clusters 2 and 5 are discussed. |
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