Subject nitrido

The nitrido and phosphido complexes of TMs have been the subjects of intensive experimental studies in the recent years. Of particular interest has been the issue of Lewis basicity of the nitrogen and phosphorus atoms in the TM=N and TM=P groups. Table 7.17 lists the BDEs calculated at the MP2/II, B3LYP/B and CCSD(T)/B levels of theory for LnMN-X and LnMP-X, where X is a group-13 Lewis acid or a chalcogen atom [86, 87]. 

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 subject of transition metal nitrido complexes has been reviewed.310,311... 

In some osmium(VI) nitrido complexes the N3 ligand is subject to nucleophilic attack by phosphines PR3 to give phosphineiminato complexes Os(NPR3)X3(PR3)2 313-315 similar complexes are formed by phosphinites.265 The formation of these is illustrated in Scheme 10 below, see also p. 568. 

Carbonylferrates have been the subject of many studies. The well-defined mono-, di-, and trinuclear species [FefCO) ", [Fe2(CO)g] , and [Fe3(CO)ii] have been obtained by a variety of methods in varying yields and degrees of convenience. The procedures described here provide uniform, convenient, high-purity, high-yield syntheses of the sodium salts of these three important reagents. In addition, the preparation of the bis [/<-nitrido-bis(triphenylphosphorusXl + )] salt of [Fe3(CO)n] by metathesis of [(Ph3P)2N]Cl with Na2[Fe3(CO)i i] is presented. 

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