| This thesis is concerned with the synthesis and coordination chemistry of analogues of common phosphorus oxo anions, e.g. orthophosphate [PO4]3-, metaphosphate [PO3] -, and phosphonate [RPO3]2-, in which the oxygen atoms are replaced by imido (NR) groups and chalcogen (S or Se) atoms. These multidentate anions display versatile coordination behavior resulting from the combination of hard (N) and soft (S or Se) donor sites. In the case of metaphosphates they provide a platform for the development of novel coordination polymers.; Treatment of the bis(amido)chalcogenido phosphonates PhP(E)[N(H) tBu]2 (E = O, S, Se) with nBuLi generates the dimers {lcub}[Li(THF)]2[PhP(E)(NtBu)2]{rcub} 2 (E = S, Se) and {lcub}(THF)Li2[PhP(O)(NtBu) 2]{rcub}4·Li2O, a Li2O-templated tetramer. The deprotonation of OP[N(H)tBu]3 with nBuLi is incomplete producing only mono- or dilithium derivatives, (THF){lcub}LiOP(NtBu)[N(H)tBu]2{rcub} 3 and {lcub}(THF)2Li2OP(NtBu)2 [N(H)tBu]{rcub}2, respectively. The reaction with ZnMe2 generates Zn(ZnMe)2{lcub}OP(NtBu)[N(H) tBu]2{rcub}[OP(NtBu)3], a complex containing the first tris(imido)phosphate trianion, [OP(N tBu)3]3-. For the tris(alkylamido)thiophosphates SP[N(H)R]3 (R = iPr, tBu) only mono- or di-lithiation is also observed and, in the case of R = tBu, further lithiation results in P--S bond cleavage. By contrast, trilithiation can be achieved for the triaryl derivatives EP[N(H)Ar]3 (E = S, Se) forming complexes that contain the first tris(imido)thio- and selenophosphate [EP(NR)3]3- (E = S, R = p-tol; E = Se, R = Ph). However, in the case of the selenium derivative, P--Se bond cleavage accompanies trilithiation at room temperature to give, as a minor product, a unique complex that incorporates Li2Se2.; The formation of alkali- and transition-metal derivatives of both the mono- and dianions, {lcub}tBuN(E)P(mu-NtBu) 2P(E)[N(H)xtBu]{rcub}2-x (E = S, Se; x = 0, 1), illustrates the ambidentate nature of these cyclodiphosph(V/V)azane ligands as they exhibit two different modes of coordination: (a) chelation via the "soft" (E, E ') and "hard" (N, N ') centers forming six-membered rings [for Na(I), K(I), Pt(II)] and (b) bis (N, E)-chelation forming four-membered rings [for Li(I), Ni(II), Pd(II), Cu(I)]. Treatment of [ tBu(H)N(Se)P(mu-NtBu)2PN(H)tBu] with KCH2Ph generates the mixed valence cyclodiphosph(III/V)azane dianion, [tBuN(Se)P(mu-NtBu)2PN tBu]2-.; These investigations provide the foundation for future study and application of these novel ligands in metal complexes with catalytic activity or as components of materials with extended structures. |
