Nitrosyls linear

Figure 11.13 Structures of polynuclear nitrosyl complexes (a) ((Cr( j -C5H5)(NO))2(M2-NH2)(M2-NO) showing linear-terminal and doubly bridging NO and (b) (Mn3( j -C5H5)3( 3-NO)3( 3-NO)] showing double-and triply-bridging NO the molecule has virtual symmetry and the average Mn-Mn distance is 250 pm (range 247-257 pm).

Ruthenium probably forms more nitrosyl complexes [115] than any other metal. Many are octahedral Ru(NO)Xs systems, where X5 can represent a combination of neutral and anionic ligands these contain a linear (or very nearly) Ru-NO grouping and are regarded as complexes of ruthenium(II). They are often referred to as (Ru(NO) 6 systems. 

Synthesis of this compound from a 15N labelled source revealed that the i4N and 15N were equally distributed between the apical bent nitrosyl (NO-) and equatorial linear nitrosyl (NO+) ... 

The pattern of behaviour in osmium nitrosyls seems to be similar to that seen with ruthenium, though fewer data are available. The most common type of complex has octahedrally coordinated osmium(II) with linear Os-N-O linkage. Some syntheses are shown in Figure 1.67. 

Many of the nitrosyls studied are 5-coordinate, and analysis of crystallographic results indicates that, in general, in the trigonal bipyramid structures NO is found in the equatorial position in a linear geometry whereas in a square pyramidal structure, there is a bent M—N—O linkage in an apical position. A further point of interest is that in compounds like Ir(NO)Cl2(PPh3)2, the nitrosyl group bends in the more hindered (P—Ir—P) plane. 

The nitrosyls RuH(NO)(PR3)3 are 5-coordinate with trigonal bipyramidal structures and linear Ru-N-O geometries the hydride and nitrosyl ligands occupy the apical positions (for RuH(NO)(PPh3)3, z/(Ru-H) 1970 cm-1, i/(N—O) 1640 cm-1 H NMR, 8 = +6.6 ppm for the hydride resonance). The high-field NMR line is a quartet showing coupling with three equivalent phosphines, which would not be possible in a square pyramidal... 

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