## Abstract

Reaction of [ReOCl_{3}(PPh_{3})_{2}] with bromophenylhydrazine in methanol yields [ReCl(N_{2}C_{6}H_{4}Br)_{2}(PPh_{3})_{2}] (1). Complex 1 reacts with arylthiolates to give mixtures of [Re(SAr)(N_{2}C_{6}H_{4}Br)_{2}(PPh_{3})_{2}] (2) and [Re_{2}(SAr)_{7}(NNR)_{2}]^{-}. Complexes 1 and 2 display trigonal bipyramidal geometries with the phosphine ligands occupying the axial sites. A significant feature of the structures is the nonequivalence of the rhenium-diazenido moieties, such that for 1 the ReN(1) and N(1)N(2) distances are 1.80(2) and 1.24(3) Å, while ReN(3) and N(3)N(4) are 1.73(2) and 1.32(3) Å, and for 2 the ReN distances are 1.73(1) and 1.80(2)° with corresponding NN distances of 1.32(2) and 1.25(2) Å. Reaction of (PPh_{4})[ReO(SPh)_{4}] (3) with unsymmetrically disubstituted hydrazines affords complexes of the type [ReO(SPh)_{3}(NMRR′)] (R = Me, R′ = Ph for 4). Complexes 3 and 4 display distorted square pyramidal geometries with the oxo groups apical. The significant feature of the structure of 4 is the nonlinear ReN(1)N(2) linkage, exhibiting an angle of 145.6(10)°. The angle does not appear to correlate with a significant contribution from a valence form with sp^{2} hybridization at the α-nitrogen. Crystal data: 1: monoclinic space group, P2_{1}/n, a = 12.216(2) Å, b = 19.098(2) Å, c = 20.257(4) Å, β = 106.20(1)°, V = 4538.3(8) Å^{3} to give Z = 4; structure solution and refinement based on 1905 reflections converged at R = 0.070. 2: monoclinic space group P2_{1}/n, a = 14.393(2) Å, b = 18.842(3) Å, c = 20.717(4)Å, β = 110.26(1)°, V = 5270.5(8) Å^{3} to give Z = 4 for D = 1.53 g cm^{-1}; structure solution and refinement based on 4249 reflections to give R = 0.070. 3: monoclinic space group P2_{1}/n, a = 12.531(2) Å, b = 24.577(4) Å, c = 16.922(3) Å, β = 99.06(1)°, V = 5146.2(9) Å^{3}, D = 1.36 g cm^{-3} for Z = 4, 2912 reflections, R = 0.050. 4: monoclinic space group p2_{1}/n, a = 16.137(2) Å, b = 9.863(2) Å, c = 16.668(2) Å, β = 111.12(1)°, V = 2474.7(6) Å^{3}, D = 1.74 g cm^{-3} for Z = 4, 2940 reflections, R = 0.066.

Original language | English (US) |
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Pages (from-to) | 1577-1585 |

Number of pages | 9 |

Journal | Polyhedron |

Volume | 6 |

Issue number | 7 |

DOIs | |

State | Published - 1987 |

Externally published | Yes |

## ASJC Scopus subject areas

- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry

## Fingerprint

Dive into the research topics of 'Monomeric five-coordinate rhenium diazenido and hydrazido complexes with aromatic thiolate ligands: X-ray structures of [Re(NNC_{6}H

_{4}-Br)

_{2}(SC

_{6}H

_{3}-2,5-Me

_{2})(PPh

_{3})

_{2}] and [ReO(NNMePh)(SPh)

_{3}], and of the synthetic precursor [Re(NNC

_{6}H

_{4}-4-Br)

_{2}Cl(PPh

_{3})

_{2}]'. Together they form a unique fingerprint.