Reactions of perfluoroalkyl-substituted phosphines with osmium carbonyl clusters: crystal structures of bridged, linked and substituted derivatives

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Abstract
The secondary phosphine (CF3)2C(OH)PH(CF3) has been shown from 1H and 19F NMR and single-crystal X-ray diffraction studies to undergo P–C bond cleavage upon reaction with [Os3(CO)11(MeCN)] to afford the phosphido-bridged cluster [Os3(µ-H)(CO)10{µ-PH(CF3)}]1 and the linked cluster [{Os3(µ-H)(CO)11}{µ-PH(CF3)}{Os3(CO)11}]2. However, its reaction with [Os3(CO)10(MeCN)2] afforded the novel molecule [Os3(µ-H)(CO)9{µ-HNC(Me)P(CF3)}]3 the molecular structure of which has also been established. Compound 1 was also obtained from the reaction of (CF3)2C(OH)PH(CF3) or PH(CF3)2 with the anionic cluster [Os3H(CO)11]–. Furthermore the primary phosphines (CF3)2C(OH)PH2 and PH2(CF3) display similar P–C bond cleavage upon reactions with [Os3H(CO)11]– to afford the phosphido-bridged cluster [Os3(µ-H)(CO)10(µ-PH2)]. On the other hand, (CF3)2C(OH)PH2 gave simple substitution products upon reactions with [Os3(CO)10(MeCN)2] and [Os3(CO)11(MeCN)], as has been found for the tertiary phosphine P(CF3)3. Compound 2 represents the first example of two triosmium triangles linked by a terminally co-ordinated PR2 group.

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