| Fac-octahedral twelve electron d6 transition metal fragment sources were used as precursors to novel organometallic cyanometallate cages and coordination solids and π-arene complexes of phthalocyanines. Cubic, tetrahedral, and trigonal prismatic molecular cages composed of transition metals linked together by bridging cyanide ligands were prepared. The cubic cages, which comprise M8(CN)12 boxes, M7(CN) 12 defect boxes, and M′{lcub}M″⊂M 7(CN)12{rcub}2 double boxes, were prepared by condensation of fac-L3M(NCMe)3z+ sources with fac-L3M(CN)3− containing kinetically inert M-CN bonds (L3=Cp, Me 4C5H, EtMe4C5, Cp*; M = Co, Rh, Ir, Ru; z = +1, +2). The cages contain ordered M-CN-M linkages. The double box species contain two alkali metal cations in the box interiors and one at the inter-box junction. The factors which influence the type of cage formed were elucidated. The M-NC bonds in these cages can be cleaved by a variety of nucleophiles including F−, Cl−, and CN −. Alkali-metal containing tetrahedral and trigonal prismatic cages with M′⊂M4(CN)6 and M ′⊂M6(CN)9 frameworks, respectively, were prepared in a multicomponent one-pot synthesis involving (mesitylene)Mo(CO)3 (a source of Mo(CO)3), cyanide, and an alkali metal salt. The size of the alkali metal cation determines the cage size: Cs+ and K+ lead to the formation of trigonal prismatic cages whereas Na+ and Li+ give tetrahedral cages.; Attempts to prepare expanded cages by reaction of Cp*Ir(CN)3 − and Cp*Rh(CN)3− with ditopic and tritopic Lewis acids such as Rh2(O2CCX3) 4 (X = H, F), H3O+, Ni(en)2 2+, Ag+, and Ag(py)+ lead to the formation of 1-D, 2-D, and 3-D coordination solids.; A related class of organometallic cyanometallates was prepared as structural models for the active site of [Fe]-hydrogenases. Complexes of formula (PPh 4)2[Fe2(SR)2(CO)4(CN) 2] ((SR)2 = (SMe)2, S2C3H 6) were prepared by reaction of Fe2(SR)2(CO) 6 with Et4NCN. Structural characterization confirmed the resemblance to the active site, including the presence of one CN− on each iron center.; Π-arene complexes of octaalkoxyphthalocyanines and metallophthalocyanines were prepared by reaction of soluble phthalocyanine (H2PcOR) and metallophthalocyanine (M(PcOR)) ligands with Cp*Ru(NCMe)3 +. The molecular structure of {lcub}Cp*Ru[η6-Ni(PcOBu)]{rcub}PF 6 consists of a dimer of two cofacially stacked {lcub}Cp*Ru[η 6-Ni(PcOBu)]{rcub}+ units. In [Cp*Ru(η6-H 2PcOEt)]PF6 the two NH protons exhibit differences in reactivity, and the N4H2 pocket can be metallated. |
