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Diazo Complexes of Rhenium:  Preparations and Crystal Structures of the Bis(dinitrogen), [Re(N2)2{PPh(OEt)2}4][BPh4] and Methyldiazenido [ReCl(CH3N2)(CH3NHNH2){PPh(OEt)2}3][BPh4] Derivatives

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Dipartimento di Chimica, Università Ca'Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy, and Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Centro CNR di Strutturistica Diffrattometrica, Università di Parma,Viale delle Scienze, 43100 Parma, Italy
Cite this: Inorg. Chem. 2000, 39, 15, 3283–3293
Publication Date (Web):July 1, 2000
Copyright © 2000 American Chemical Society

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    Depending on experimental conditions and the nature of the hydrazine, the reactions of ReCl3P3 [P = PPh(OEt)2] with RNHNH2 (R = H, CH3, tBu) afford the bis(dinitrogen) [Re(N2)2P4]+ (2+), dinitrogen ReClN2P4 (3), and methyldiazenido [ReCl(CH3N2)(CH3NHNH2)P3]+ (1+) derivatives. In contrast, reactions of ReCl3P3 [P = PPh(OEt)2, PPh2OEt] with arylhydrazines ArNHNH2 (Ar = Ph, p-tolyl) give the aryldiazenido cations [ReCl(ArN2)(ArNHNH2)P3]+ (4+) and [ReCl(ArN2)P4]+ (7+) and the bis(aryldiazenido) cations [Re(ArN2)2P3]+ (5+, 6+). These complexes were characterized spectroscopically (IR; 1H and 31P NMR), and the BPh4 complexes 1, 2, and 7 were characterized crystallographically. The methyldiazenido derivative [ReCl(CH3N2)(CH3NHNH2){PPh(OEt)2}3][BPh4] (1) crystallizes in space group P1̄ with a = 15.396(5) Å, b = 16.986(5) Å, c = 11.560(5) Å, α = 93.96(5)°, β = 93.99(5)°, γ = 93.09(5)°, and Z = 2 and contains a singly bent CH3N2, group bonded to an octahedral central metal. One methylhydrazine ligand, one Cl- trans to the CH3N2, and three PPh(OEt)2 ligands complete the coordination. The complex [Re(N2)2{PPh(OEt)2}4][BPh4] (2) crystallizes in space group Pbaa with a = 23.008(5) Å, b = 23.367(5) Å, c = 12.863(3) Å, and Z = 4. The structure displays octahedral coordination with two end-on N2 ligands in mutually trans positions. [ReCl(PhN2){PPh(OEt)2}4][BPh4] (7) crystallizes in space group P21/n with a = 19.613(5) Å, b = 20.101(5) Å, c = 19.918(5) Å, β = 115.12(2)°, and Z = 4. The structure shows a singly bent phenyldiazenido group trans to the Cl- ligand in an octahedral environment. The dinitrogen complex ReClN2P4 (3) reacts with CF3SO3CH3 to give the unstable methyldiazenido derivative [ReCl(CH3N2)P4][BPh4]. Reaction of the methylhydrazine complex [ReCl(CH3N2)(CH3NHNH2)P3][BPh4] (1) with Pb(OAc)4 at −30 °C results in selective oxidation of the hydrazine, affording the corresponding methyldiazene derivative [ReCl(CH3NNH)(CH3N2)P3][BPh4] (8). In contrast, treatment with Pb(OAc)4 of the related arylhydrazines [ReCl(ArN2)(ArNHNH2)P3][BPh4] (4) [P = PPh(OEt)2] gives the bis(aryldiazenido) complexes [Re(ArN2)2P3][BPh4] (5). Possible protonation reactions of Brønsted acids HX with all diazenides, 1, 4, 5, 6, and 8, were investigated and found to proceed only in the cases of the bis(aryldiazenido) complexes 5 and 6, affording, with HCl, the octahedral [ReCl(ArNNH)(ArN2)P3][BPh4] or [ReCl{Ar(H)NN}(ArN2)P3][BPh4] (10) (Ar = Ph; P = PPh2OEt) derivative.

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     Università Ca'Foscari di Venezia.

     Università di Parma.

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    X-ray crystallographic files, in CIF format, for the structure determinations of complexes 1, 2, and 7. This material is available free of charge via the Internet at

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