Amides of the Group 15 Metals As, Sb, Bi

In Part 2 of the book, reference was made to RNCO insertions into M NR2 (M = As, mainly but also M = Sb or Bi). Protolytic cleavage of M -NR2 bonds was reported for a number of As but very few Sb or Bi amides. Metathetical exchange reactions (principally NMe2/Cl exchanges) were established for a number of As amides but just two Sb or one Bi amide. As(NMe2)3 (= L) was shown to be a ligand in [Ni(CO)3(L)] [As(Cl)(p-NBu )]2 was obtained by thermal reductive elimination from [As(Cl)3(=NBu )]. 

The majority of amides (or imides) of arsenic, antimony and bismuth (collectively designated as of M ), have M in the - -3 oxidation state, although several examples of As and Sb amides or imides have been reported but only three papers have dealt with Bi compounds. The imides considered to be within the scope of this chapter are those having trivalent nitrogen as, for instance, in [As(p-NR)X]2. There are very few examples of As —N compounds, such as the bis(imido)arsenic(I) cation 1, and only one of a thermally stable 

Metal Amide Chemistry Michael Lappert, Andrey Protchenko, Philip Power and Alexandra Seeber 

An article on Coordination complexes of bismuth(in) involving organic ligands with pnictogene or chalcogene donors has a brief (9 refs.) section on amidobismuth(ni) compounds. 2 

In earlier work, no molecular structural data were available on mononuclear M amides, but this has changed markedly in the last three (and particularly last two) decades. Another significant development has been the use of the title compounds, and especially the homoleptic dimethylamides M(NMe2)3, as reagents, or synthons for the preparation of bridging binuclear imides 7 (Section 10.3) or cluster imides (e.g. 3 7) (Section 10.4), or Bi[N(SiMe3)2]3 as a precursor for atomic layer deposition.Heteroleptic amidometal chlorides have featured as precursors to cationic metal(III) amides (Section 10.2.4). 

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Amides of the Group 15 Metals (As, Sb, Bi) 337 Table 10.4 Comparative M-N bond lengths (A) for two pairs of compounds... 

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