Abstract
The clusters (μ 3-RP) 2Fe 3(CO0 9 ( 1) photochemically add alkines R′CCR′ across their bridging phosphorus centers to yield (μ 3-η 4-RPCR′CR′PR)Fe 3(CO) 9 ( 2). Thermal activation of 2 opens two different reaction channels: Complezes 2 may split into R′CCR′ and 1 in a thermally induced reversion of their photoinitiated formation reaction: in another pathway they may lose Fe(CO) 3 to yield (μ 2-η 2-(PFe)RPCR′CR′PR)Fe 2(CO) 6 ( 3). Complex 3 is an Fe 2(CO) 6 derivative of the butterfly type with the μ 2-bridging phosphorus centers linked by an R′CCR′ moeity. The reverse transformation 3 → 2 is induced by Fe 2(CO) 9 as an “Fe(CO) 3” source. Compounds 2 undergo a CO substitution reaction with R′CCR′ to give (μ 3-η 2- RPCR′CR′PR)(μ 3-η 2-R′CCR′)Fe 3(CO) 7 ( 4) which, upon heating, also transforms into 3. The above reactions 1 ⇋ 2 ⇋ 3 and 2 → 4 → 3 ⇋ 2 present a rare example of a complete closed set of cluster transformations. An analogous subset of reactions is also verified for the arsenic homologues 1, 2 and 4.
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