Molybdenum complexes, with nitrosyl

These complexes are generally prepared by methods similar to those employed for the dinitrosyl compounds, treatment of a low-valent molybdenum compound with NO or a nitrosyl derivative being the principal method. Compounds and major physical properties are collected in Table 3. 

The amido nitrosyl molybdenum complex MoCI(Tp )(NO)-(NH2)] reacts with alcohols, yielding the bisalkoxo complexes [Mo(OR)2(Tp )(NO)] (R = Me, Et, "Pr, Bu), analyzed by IR and H-NMR spectroscopy.60 Topaloglu and McCleverty also reported the synthesis and characterization of amido- and amido(monoalkylamido)-Mo(Tp )(NO) species61 and of [MoCl-(Tp )(NO)(OC6H4PPh 2-p)].62... 

The nitrosyl carbonyls CpM(NO)(CO)2 [M=Cr (21, 7S), Mo (57), W (19)) can be made by the action of nitric oxide on [CpCr(CO)3]2, [CpMo(CO)3] , or [CpW(CO)3] , respectively. The chromium complex undergoes a Friedel-Crafts acetylation to give (CsH4COCH3)Cr(NO)(CO)2 (21). A series of molybdenum complexes CpMo(NO)l2L [L = PPh3, P(OPh)3, py, and bipy] has been made from L and [CpMo(NO)l2]2 (57). The cationic manganese species [CpMn(NO)(CO)2], obtained by the action of nitrite and acid on CpMn(CO)3, can be precipitated as the yellow hexafluorophosphate salt (51). With sodium borohydride this affords [CpMn(NO)(CO)]2 which probably contains bridging NO groups (see below) (58). The complex [CpMn(NO)S2] is probably similar in structure... 

The analogous reaction of 3 with W2(OrBu)6 gave a brown solution, from which a yellow, microcrystalline material could be isolated. Based on spectroscopic data the latter was formulated as [Cy7Si70i2]2W2(p-H)(0tBu) (158). Cleavage of the Mo = Mo triple bond in 157 occurred upon treatment of this compound with NO (two equivalents) to afford the dimeric nitrosyl molybdenum silsesquioxane complex [Cy7Si70i2]2Mo2(NO)2 (159). °°... 

Second, the results obtained from the MoCl2(NO)2(4-Etpy)2/ (CH3)3A12C13 system indicate that the interaction of organoaluminum and complex occurs in several stages. A rapid, initial step in which the vN0 bands are shifted to higher frequency is followed by a slower step in which the first-formed species is converted to a second nitrosyl species with vno bands at lower frequencies and a final step in which the NO groups are lost from the molybdenum. 

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... 

The electrochemical transformation of a molybdenum nitrosyl complex [Mo(NO)(dttd)J [dttd = 1,2-bis(2-mercaptophenylthio)ethane] (30) is rather interesting (119). Ethylene is released from the backbone of the sulfur ligand upon electrochemical reduction. The resulting nitrosyl bis(dithiolene) complex reacts with O2 to give free nitrite and a Mo-oxo complex. Multielectron reduction of 30 in the presence of protons releases ethylene and the NO bond is cleaved, forming ammonia and a Mo-oxo complex (Scheme 15). The proposed reaction mechanism involves successive proton-coupled electron-transfer steps reminiscent of schemes proposed for Mo enzymes (120). 

Bimetallic molybdenum nitrosyl complexes, (containing Mo(I), i.e. a 17e species) with conjugated bridging ligands of the bispyridine family, or the bisphenolate family, present widely separated reduction waves, as shown by McCleverty, Ward, and others [86], The separation can be observed with spacers containing up to four double bonds, or four phenylene units. 

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