Bis(1Њ-amino)cyclodiphosph()azanes and bis(1Њ-amino)cyclodiphosph()azanes show different coordination preferences with titanium(). The bis(tert-butylamino)cyclodiphosph()azane cis-[Bu t (H)N(Bu t NP) 2 N(H)Bu t ] (1) reacts with TiCl 4 to afford {[(Bu t NP) 2 (NBu t ) 2 ]TiCl 2 } (2), in which the ligand chelates the metal as a diamide, above the heterocycle. Oxidations of 1 with phenyl-or p-tolyl azide yield the cyclodiphosph()azanes cis-[Bu t (H)N(ArN᎐ ᎐ PNBu t ) 2 N(H)Bu t ] (Ar = phenyl (3), p-tolyl (4)). Single-crystal X-ray studies of 3 and 4 reveal structures similar to those of their parent cyclodiphosph()azanes, but with pendent arylimino groups attached to the phosphorus() atoms. When 3 and 4 are allowed to react with TiCl 4 the complexes {[Bu t (H)N(ArN᎐ ᎐ PNBu t ) 2 NBu t ]TiCl 3 } (Ar = phenyl (5), p-tolyl (6)) are isolated. In these compounds the cyclodiphosph()azanes coordinate the metal laterally as monoanionic N-P-N ligands, similar to phosphoranates. An analogous side-on coordination is also found for the dichalcogeno complexes {[Bu t (H)N(E᎐ ᎐ PNBu t ) 2 NBu t ]TiCl 3 } (E = S (9), Se (10)).

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Nickel(ii) chloride reacts with the bis(tert-butylamino)diazadiphosphetidine {Bu(t)(H)NP(micro-NBu(t))(2)PN(H)Bu(t)} to form trans-[{Bu(t)(H)NP(micro-NBu(t))(2)PN(H)Bu(t)}(2)NiCl(2)]. In solution and the solid-state each heterocyclic ligand coordinates nickel through one phosphorus atom only. For comparison the solid-state structure of the known trans-[NiCl(2)(PEt(3))(2)] was also determined and it was found that the two complexes have almost identical bond parameters about nickel. The nickel-amidophosphine complexes [{Bu(t)OP(micro-NBu(t))(2)PNBu(t)}NiCl(PBu(n)(3))], [(PBu(n)(3))ClNi{Bu(t)NP(micro-NBu(t))(2)PNBu(t)}NiCl(PBu(n)(3))], and [{Me(2)Si(micro-NBu(t))(2)PNBu(t)}NiCl(PBu(n)(3))] were synthesized and X-ray structurally characterized. In these mono- and di-nuclear nickel complexes the nickel ions are coordinated in pseudo square-planar fashions, by one trialkylphosphine ligand, one chloride ligand and one kappaP,N-coordinated amidophosphine moiety from tert-butylamido-substituted heterocycles. Attempts to create nickel complexes chelated in a kappa(2)P fashion by the o-phenylenediamine-tethered mono- and di-anionic 1-{Me(2)Si(micro-NBu(t))(2)PN} 2-{Me(2)Si(micro-NBu(t))(2)PNH}C(6)H(4) and 1,2-{Me(2)Si(micro-NBu(t))(2)PN}C(6)H(4), respectively, afforded instead [1,2-{Me(2)Si(micro-NBu(t))(2)PN}{Me(2)Si(micro-NBu(t))(2)PN}C(6)H(4)NiCl] and [1,2-{Me(2)Si(micro-NBu(t))(2)PN}{Me(2)Si(micro-NBu(t))(2)PN}C(6)H(4)Ni{PEt(3)}], each complex having kappaP,N and kappaP coordinated amidophosphine ligands.

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