Azo-phosphine containing complexes of Group 6 metal carbonyls: crystal and molecular structure of [Mo(CO)5{1-(4-ethylphenylazo)-6-diphenylphosphino-naphthalen-2-ol}]
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文摘
Treatment of the compounds [M(CO)5(NCMe)] (M=Cr, Mo, W) with the phenylazonaphthylphosphines 4-R–PhN2-1-C10H5-2-OR′-6-PPh2 {R′=H, R=H (I), R=Me (II), R=Et (III), R=Pri (IV) R=But (V); R′=C(O)Me, R=Me (VI)} afforded the mono-substituted products [M(CO)5(L)] (1-8) (M=Cr, L=II, 1; M=Mo, L=I–VI, 2–7; M=W, L=II, 8). Further reaction of cis-[Mo(CO)4(piperidine)2] with the azo-phosphines I–V afforded the di-substituted complexes cis-[Mo(CO)4(L)2] (9–13); whereas, reaction with VI afforded cis-[Mo(CO)4(II)2] 10 rather than the expected compound cis-[Mo(CO)4(VI)2] (14). 14 can, however, be prepared by esterification of 10. The observed non-innocence of piperidene on displacement from cis-[Mo(CO)4(piperidine)2] has been further investigated. Thus, treatment of 7 with piperidene yielded 3 as a result it becomes apparent that the potential reactivity of the displaced ligand needs to be considered carefully when carrying out simple substitution reactions. The molecular structure of 4 is also reported.