Of isocyanide complexes

Recent advances in the chemistry of isocyanide complexes. F. Bonati and G. Minghetti, Inorg. Chim. Acta, 1974, 9, 95-112 (238). 

The reaction of isocyanide complexes with nucleophiles gives metal-carbene complexes [49], which constitute an important branch of organometallic chemistry and are effective catalyst systems for a variety of processes [50, 51]. 

A less conventional preparation of isocyanide complexes involves the reaction of iron pentacarbonyl with metalated (sodium or lithium derivative) hexamethyldisilazane (162). 

A general procedure has been outlined for the preparation of isocyanide complexes of Wn (equations 23, 24).316 [W(CNR)7]2+ (R = CMe3, C6HU) can also be prepared by reaction of the... 

Simple oxidation/reduction has also been studied for a wide range of isocyanide complexes. Again those complexes containing mainly molybdenum-carbon bonds have been reviewed in... 

A number of isocyanide complexes, [Mo(CN)4(CNR)4] (R = Me, Pr, Bu allyl, NCPh2), have been made by the action of RI on Ag4[Mo(CN)8]. The crystal structure of [Mo(CN)4(CNMe)4] shows a dodecahedral geometry, with the CN- ligands at 2.177(8) A and the MeNC ligands at 2.148(8) A from the molybdenum.207 Both 13C NMR and vibrational spectroscopy indicate that only one isomer is present in solution. 

Other examples of isocyanide complexes formed from cyanide alkylations are [CpFe(CO)(CNEtXPPh3)]+ (83), fram-[Pt(CNMe)2(PMe2Ph)2]-(SF03)2 (84), and PtI2(CNMe)2 (85). 

Formation of isocyanide complexes of molybdenum(II) starting from Mo,4 derivatives... 

Finally, although not a reaction of isocyanide complexes as such, except as labile intermediates, it can be noted that metal hydrido or alkyl compounds can undergo insertion reactions to give acylimidoyl complexes, which can react further ... 

Isocyanides.—Specific types of isocyanide complexes have been reviewed. Formation of MoCl4(MeCN)2, MoBr3(MeCN)3, and WX4(MeCN)2 (X = Cl or Br) was found to occur upon oxidation of/ac-M(CO)3(MeCN)3 by the appropriate halogen. Synthesis of the molybdenum isocyanide complexes Mo(CO), (CNCH2MMe3)j (x = 1,2, or 3 M = Si, Ge, Sn, or Pb) has been accomplished and the inductive effect of the Me3M- group determined from i.r. data. ... 

The electronic spectra of isocyanide complexes [Pt(CNR)4]X2 show intense charge transfer bands in the UV region caused by MLCT to a jr orbital. The d-d bands have been assigned to... 

Displacement of ligating dinitrogen by isocyanides constitutes a convenient route for the preparation of isocyanide complexes. The first isocyanide complexes prepared by this route involve a molybdenum(0) or tungsten(0) electron-rich metal site, and the general method for their synthesis is given below. 

The number of stretching vibrations v(C = N) and ratios of their intensities furnish information regarding the structure of isocyanide complexes. The selection rules are... 

Reactions of metal cyanides with various compounds leading to the preparation of isocyanide complexes have less significance at present, because synthetic methods that utilize isocyanides as substrates have been developed. Nevertheless, metal cyanides are still used in the case of synthesis of complexes with unstable or unattainable isocyanides... 

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