Nitrosyl complexes halides

The full account of the preparation and subsequent reactions of the cationic nitrosyl complexes [M(NO)(CO)3(diphos)]PF6 (M = Mo or W) has been published. These complexes react with NaX (X = halide, S2CNMe2, or S2CNEt2) salts to form the corresponding [M(NO)(CO)2(diphos)X] derivative. With phosphine ligands (L) in CHC13, [M(NO)(CO)L(diphos)Cl] is obtained, but in acetone, [M(NO)(CO)2L2-(diphos)](PF6),(acetone) and [M(NO)(CO)(diphos)2](PF6) are formed. Decarbonyla-tion occurs when [Mo(NO)(CO)3(diphos)](PF6) is heated under reflux in CHC13 to produce [Mo(NO)(diphos)Cl2] and other polynuclear nitrosyl species.320... 

Several iridium( —I) nitrosyl complexes are known. Those with the general formula [Ir(NO)2X(PPh3)2] (X = Cl, Br, I) are produced upon reduction of [Ir(NO)2(PPh3)2] with the appropriate lithium halide. IR spectral data for these complexes indicate bridging NO groups, as shown by the low N—O frequencies [v(N—O) 1540-1490 cm-1].7 Reaction of [Ir(NO)2X(PPh3)2] with NO results in the oxidation of NO according to reaction (l).8... 

PF3-containing transition metal nitrosyl complexes such as [Co(NO)(PF3)3] and [Fe(NO)2(PF3)2] were first prepared by Kruck and Lang (206, 207) by reduction of dimeric nitrosyl halide complexes with copper in the presence of PF3 (method A). 

A very large series of nitrosyl complexes, [Mo(NO)Tp X Y] has been described where X and Y are halide, alkoxide, aryloxide, alkyl or arylamide, alkyl or aryl thiolate groups. These diamagnetic Mo(NO) + species are regarded as containing 16 valence electrons, with a formal metal oxidation state of 11, assuming NO+ binding, and the metal center could... 

Nitrosyl complexes are rather numerous and [Re(NO)Xs] is known for all the halides (= X) addition of phen or bipy (= L-L) gives [Re(NO)X3(L-L)] or of pyridine, alcohols, DMSO, or MeCN (= solv) gives [Re(NO)X4(solv)] PPhs in EtOH followed by NaBH4 gives the nitrosyl hydride [ReH2(NO)(PPh3)3]. Other nitrosyl complexes include [Re(NO)Cl2(OMe)(PPh3)2] and [Tc(NO)Br4] and the low-valent complexes indicated above. 

A number of metal nitrosyl complexes react with activated alkyl halides to yield, ultimately, organic nitrogen-containing products. The most widely studied reagent is [Ru(NO)2(PPh3)2] (229), though other compounds such as [CoCl(NO)(CO)2] (230) and [Fe(NO)(CO)3] (231) have been used. These reactions have been discussed in depth elsewhere (6). Another reaction of some industrial importance is the catalytic reaction of NO gas with alkenes. Over Ag20 or PbO the product from propene is acrylonitrile. In a study of this type of reaction (232),... 

A. Organometallic Complexes Halide Complexes and Clusters Complexes with Nitrogen Ligands Phosphine, Arsine, and Related Complexes Complexes with Sulfur Ligands Nitrosyl and Thionitrosyl Complexes Technetium(III)... 

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