Molybdenum nitrido complexes

Several nitrido complexes of W5 1 are known. WCU reacts with C1N377 to give [WNC13] whose structure is believed to be tetrameric similar to that of its molybdenum analogue.78 [WNCI3]... 

The first thionitrosyl complex was discovered by chance during an attempted synthesis of molybdenum nitrido complexes in the presence of a source of sulfur, tetrathiuram sulfide.168 This work of Dilworth and Chatt was reported in 1974 and ultimately led to the syntheses of a range of Mo, Re and Os thionitrosyl complexes starting with the respective nitrido complexes.143,164 Nitrosyl complexes, like carbonyls, had been known for decades, and the more recent syntheses of thio-carbonyl complexes forebode the advent of thionitrosyl complexes. However, convenient synthetic routes based on analogies with syntheses of NO complexes were generally not available because the requisite precursors did not exist or were inconvenient to handle. Sulfiliminato complexes (M=N=SR2) of transition metals are as yet unknown. The chemistry of thionitrosyl complexes was the subject of a recent review.179... 

This method has been used most widely, but it is limited to the availability of reactive nitrido complexes. The molybdenum nitrides simply abstract sulfur from episulfides (MeCHCH2S) or... 

Imido-nitrido complexes, with mono-Cp Ti(IV), 4, 425-426 Imido-supporting ligands, in molybdenum complexes alkenes, 5, 535 alkynes, 5, 548... 

The complex is air sensitive in the solid state and almost insoluble in THF, but soluble in dichloromethane. It deteriorates even under nitrogen when stored for a period of weeks and is best used immediately for subsequent syntheses. Its IR spectrum shows an intense band at 820 cm-1, characteristic of coordinated THF. The complex can be used to prepare other molybdenum(IV) complexes by displacement of the THF ligands7 or molybdenum (VI) nitrido complexes by reaction with trimethyMyl azide.8... 

The orange complex is air sensitive in the solid state. It is reasonably soluble and stable in THF but decomposes in nonpolar solvents, such as benzene, to give polymeric halogen-bridged products.9 It is paramagnetic with a magnetic moment of 3.63 BM, and its IR spectrum shows a very intense band at about 820 cm-1 due to coordinated THF. Its reactions with tertiary phosphines in THF give a series of molybdenum (III) tertiary phosphine complexes,9 and with trimethyl-silyl azide Mo(V) nitrido complexes are formed.8... 

NMR resonances of the alkylidyne carbon atom and selected IR absorptions for new carbyne complexes are given in Table 11. In other studies, the Mo and NMR spectra of molybdenum and tungsten alkylidyne complexes were determined by Enemark and co-workers (23). The metal atoms in the alkylidyne complexes were found to be less shielded than those in nitrido complexes but more shielded than those in compounds containing metal-metal multiple bonds. 

Nitrido complexes have also been formed by metathesis and atom transfer processes. The reaction of dinitrogen with a molybdenum(III) species forms a molybdenum-nitrido complex, as shown in Equation 13.103. and described in more detail in the section of Chapter 5 on dinitrogen complexes. In a metathesis process involving related complexes, the reaction of a metal-alkylid)me complex with a nitrile extrudes an alkyne to form a metal nitride fliat adopts a dimeric structure (Equation 13.104). - Related nitrido complexes have been formed from an azabicydic compoimd that eliminates anthracene after forming the M-N bond (Equation 13.105). ... 

A. Neuhaus, A. Veldkamp, and G. Frenking, Inorg. Chem., 33, 5278 (1994). Oxo and Nitrido Complexes of Molybdenum, Tungsten, Rhenium and Osmium. A Theoretical Study. Theoretical Studies of Inorganic Compounds. IV. 

Figure 20.9 (a) Protonation and reduction of an immobilized moiybdenum(Vi) nitrido complex 43 to the imido molybdenum(V) complex 44 and (b) immobilized Schiff base vanadyl complex 45. 

Scheme 45 Photoinduced formation of an molybdenum(IV) nitrido complex. ... 

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