PhNCO reacts with oxo ligands at metal centers to form phenyl nitrene complexes. As an intermediate of this reaction we obtained with ReO2I(PPh3)2 (1) the trimeric complex [ORe(OCONPh)I(PPh3)]3 (2) in which the PhNCO moiety was added to an oxo ligand to form an N -phenyl carbamato group. This group acts as a bridging ligand chelating one Re atom via its N and one O atom and coordinating an other Re atom by its second O atom . 2 crystallizes as 2 · 2 CHCl3 in the triclinic space group P1̄ with a = 1423.1(5), b = 2443.3(7), c = 1403.8(6) pm , α = 92.31(3), β = 94.76(3), γ = 81.48(3)°, and Z = 2. From the mother liquor of 2 after a few days Re(NPh)(NH2Ph)I2(PPh3)(OCONHPh) (3) is formed as a partial hydrolysis product. 3 is monoclinic with the space group P21/n and a = 1163.0(4), b = 2527.0(3), c = 1243.9(5) pm, β = 98.04°, Z = 4. The Re atom exhibits an octahedral coordination w ith the two I atom s in a ?ra«s-arrangem ent and the phenyl nitrene ligand trans to the m onodentate PhN HCO2 group. The coordination is completed by a phosphine and an aniline ligand. Reaction of 2 with excess PPh3 yields 1. It crystallizes from CHCl3 as 1 · CHCl3 in the monoclinic space group P21/n with a = 975.9(3), b = 2731(1), c = 1417.3(6) pm , β = 93.35° and Z = 4. In 1 the Re atom is pentacoordinated in form of a trigonal bipyram id with the two phosphine ligands in axial positions. A solution of 2 in THF forms Re(NPh)(NH2Ph)I2(PPh3) (OReO3) (4) upon exposure to air at room temperature. 4 is obtained as orthorhombic crystals with the space group Pca21 and a = 1727(1), b = 1064.2(4), c = 1765.7(9) pm , Z = 4, and is an analogue of 3 from which it can be derived by substituting the carbamato ligand by a perrhenat ion. In 3 and 4 the phenyl nitrene ligand is bound by a Re = N triple bond of 172 pm in a linear arrangement Re = N - Ph .
