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Mono- and Bis-diazenido Complexes of Rhenium(III) containing Bidentate Ditertiary Phosphine Ligands. The Crystal and Molecular Structures of *2dmf, and

DOI: 10.1039/DT9950001663

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1663 - 1670 (1995)

Update date:2022-08-04

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Authors:

Coutinho, BrianCoutinho, Brian

Dilworth, Jonathan R.Dilworth, Jonathan R.

Jobanputra, PannaJobanputra, Panna

Thompson, Russell M.Thompson, Russell M.

Schmid, SiegbertSchmid, Siegbert

et al.et al.

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Article abstract of DOI:10.1039/DT9950001663

Reaction of the Ru(III) bis-diazenido starting materials (X = Cl 1 or Me 2) with excess dppe (Ph2PCH2CH2PPh2) in methanol-toluene under reflux gave the novel orange-brown, formally 20-electron Re(III) bis-diazenido cations (1+) (X = Cl or Me) in good yield by addition of a suitable anion to the cooled reaction mixture.Reaction of 1 and 2 with the more reducing dmpe (Me2PCH2CH2PMe2) ligand gave the formally 20-electron bis-diazenido cation (1+) for X = Cl but the 18-electron mono-diazenido cation (1+) for X = Me.The structures of complexes *2dmf (dmf = dimethylformamide) 5. 6 and 7 have been determined: 5, triclinic, space group P<*>, a = 13.046(3), b = 13.250(3), c = 12.233(4) Angstroem, α = 110.74(2), β = 95.86(2), γ = 115.83(2) deg, Z = 1, R = 0.040; 6 monoclinic, space group P21/c, a = 8.992(2), b = 21.947(2), c = 18.982(2) Angstroem, β = 91.45(1) deg, Z = 4, R = 0.056; 7 orthorhombic, space group Pnma, a = 19.298(2), b = 11.327(2), c = 13.960(2) Angstroem, α = β = γ = 90 deg, Z = 4, R = 0.042.All three complexes have pseudo-octahedral co-ordination with four P donors in a planar equatorial array.The M-N-N angle of the diazenide ligands is found to be dependent on the steric requirements of the diphosphine ligands, the smaller dmpe ligand permitting the M-N-N angles in 6 to decrease to 147.3(5) and 149.0(4) deg compared to values of around 162.7(2) deg for the dppe complex 5.Reaction of with the arylhydrazine hydrochloride 4-MeC6H4NHNH2*HCl in CH2Cl2 in the presence of SiMe3Cl and pyridine (py) gave the new hydrazide 2(py)>.Subsequent reaction with PPh3 in MeOH gave the Re(III) diazenide , and overall this provides a route for the synthesis of Re diazenides directly from perrhenate.

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Product name:[Re(NNC6H4Cl-4)2(1,2-bis(dimethylphosphino)ethane)2]PF6

Cas No:165289-18-9

165289-18-9

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