Transition-metal derivatives phosphorus-containing

Examples of organometallic polymers containing both phosphorus atoms and transition metals in the backbone include polyferrocenylphosphines 8 (and the corresponding phosphine sulfides 9), which are accessible via the thermal ROP of phosphorus-bridged [1] ferrocenophanes [16,17]. Polymers of this type have been previously prepared by condensation routes and the catalytic potential of some of their transition metal derivatives has already been noted [18]. Living anionic ROP of phosphorus-bridged [l]ferrocenophanes has recently been demonstrated and provides a route to block copolymers such as 10 (PI = poly-isoprene) [19] ... 

Fluorophosphines are tervalent phosphorus compounds containing phosphorus-fluorine bonds and they often show markedly different chemical behavior compared with other halogenophosphines. This article is mainly concerned with recent advances in the chemistry of derivatives of PF 3 of the type PF3 X , with particular reference to (a) synthesis of new structural types, (6) the role of fluorophosphines as ligands, particularly in transition metal complexes, and (c) nuclear magnetic resonance (NMR) studies. 

Two significant surveys are published in the sane edition of Coordination Chemistry Reviews. Oxygen donor-ligand derivatives of tri-osmium dodecacarbonyl are covered by Frauenhoff and the reactions of transition metal dihydrogen complexes (of which many are carbonyl-containing) are outlined by Jessop and Morris. The crucial role of matrix Isolation studies is well covered in this article. A shorter review of interest here has been published on the role of the phosphorus d-orbitals in M-P bonding. ... 

Palladium complexes with an heterocyclic N-containing ligand have been used in the carbonylation of aromatic nitro compounds with cocatalysts such as cyclopentadienyl halides or oxyhalides of transition metals belonging to group V e.g. CP2VCI) [168], a cyclopentadienyl halide or oxyhalide together with phosphorus oxytrichloride [169], or a 1,3-diketone derivative of vanadium [170], even also in the presenee of phosphorus oxychloride [171]. 

More remarkably, structurally well-characterized Phen-containing transition metal complexes have been prepared and further applied in challenging organic transformations. Thus, cationic palladium complexes of t)fpe Pd(phen)2X2 (where X = CF3SO3, PFs, BF4) are very stable and found fairly active in combination with either benzoic acids or phosphorus acids as cocatalysts in the conversion of nitroarenes to the corresponding carbamate derivatives. Extensive studies have evidenced the key role of the nature of counteranion X of such Phen-based catalysts in the reaction outcome and even metaUacycles of type A have been isolated and identified as active intermediates in the reductive carbonyla-tion of nitrobenzene (eq l). ... 

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