Albertin Gabriele, Antoniutti Stefano, Bacchi Alessia, Bordignon Emilio, Busatto Fabio, Pelizzi Giancarlo
Dipartimento di Chimica, Università 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.
Inorg Chem. 1997 Mar 26;36(7):1296-1305. doi: 10.1021/ic9608612.
Aryldiazene complexes [Mn(CO)(3)(ArN=NH)P(2)]BF(4) (1, 2) and {Mn(CO)(3)P(2)}(2)(&mgr;-HN=NArArN=NH)(2) (3, 4) [P = PPh(OEt)(2), PPh(2)OEt; Ar = C(6)H(5), 2-CH(3)C(6)H(4), 4-CH(3)C(6)H(4), 4-CH(3)OC(6)H(4); ArAr = 4,4'-C(6)H(4)C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)C(6)H(3)(2-CH(3)), 4,4'-C(6)H(4)CH(2)C(6)H(4)] were prepared by reacting hydride species MnH(CO)(3)P(2) with the appropriate aryldiazonium cations in CH(2)Cl(2) or acetone solutions at -80 degrees C. The compounds were characterized by IR, (1)H and (31)P NMR spectra (with (15)N isotopic substitution), and a single-crystal X-ray structure determination. The complex [Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4) (1c) crystallizes in the space group C2/c with a = 31.857(5) Å, b = 11.119(2) Å, c = 22.414(3) Å, beta = 97.82(1) degrees, and Z = 8. Treatment of aryldiazene compounds 1-4 with NEt(3) gave the pentacoordinate aryldiazenido [Mn(CO)(2)(ArN(2))P(2)] (5, 6) and [{Mn(CO)(2)P(2)}(2)(&mgr;-N(2)ArArN(2))] (7, 8) [P = PPh(OEt)(2), PPh(2)OEt; Ar = C(6)H(5), 4-CH(3)C(6)H(4); ArAr = 4,4'-C(6)H(4)C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)C(6)H(3)(2-CH(3))] derivatives. Protonation reactions of these aryldiazenido complexes 5-8 with HCl afforded the aryldiazene [MnCl(CO)(2)(ArN=NH)P(2)] (9) and [{MnCl(CO)(2)P(2)}(2)(&mgr;-HN=NArArN=NH)] (10) derivatives. Hydrazine complexes [Mn(CO)(3)(RNHNH(2))P(2)]BPh(4) (11, 12) [P = PPh(OEt)(2), PPh(2)OEt; R = H, CH(3), C(6)H(5), 4-NO(2)C(6)H(4)] were prepared by allowing hydride species MnH(CO)(3)P(2) to react first with triflic acid and then with the appropriate hydrazine. Their characterization by IR, (1)H and (31)P NMR spectra, and an X-ray crystal structure determination is reported. The compound [Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(2)]BPh(4) (11a) crystallizes in the space group P&onemacr; with a = 13.772(3) Å, b = 14.951(4) Å, c = 13.319(3) Å, alpha = 104.47(1) degrees, beta = 100.32(1) degrees, gamma = 111.08(1) degrees, and Z = 2. Oxidation reactions of hydrazine compounds 11 and 12 with Pb(OAc)(4) at -40 degrees C gave stable aryldiazene [Mn(CO)(3)(RN=NH)P(2)]BPh(4) and thermally unstable (upon reaching -40 degrees C) diazene [Mn(CO)(3)(HN=NH)P(2)]BPh(4) derivatives.
芳基重氮配合物[Mn(CO)(3)(ArN=NH)P(2)]BF(4)（1, 2）和{Mn(CO)(3)P(2)}(2)(μ-HN=NArArN=NH)(2)（3, 4）[P = PPh(OEt)(2), PPh(2)OEt；Ar = C(6)H(5), 2-CH(3)C(6)H(4), 4-CH(3)C(6)H(4), 4-CH(3)OC(6)H(4)；ArAr = 4,4'-C(6)H(4)C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)C(6)H(3)(2-CH(3)), 4,4'-C(6)H(4)CH(2)C(6)H(4)]是通过在-80℃下，使氢化物MnH(CO)(3)P(2)与适当的芳基重氮阳离子在CH(2)Cl(2)或丙酮溶液中反应制备的。这些化合物通过红外光谱、(1)H和(31)P核磁共振谱（采用(15)N同位素取代）以及单晶X射线结构测定进行表征。配合物[Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4)（1c）以空间群C2/c结晶，a = 31.857(5) Å，b = 11.119(2) Å，c = 22.414(3) Å，β = 97.82(1)°，Z = 8。用NEt(3)处理芳基重氮化合物1 - 4得到五配位芳基重氮基[Mn(CO)(2)(ArN(2))P(2)]（5, 6）和[{Mn(CO)(2)P(2)}(2)(μ-N(2)ArArN(2))]（7, 8）[P = PPh(OEt)(2), PPh(2)OEt；Ar = C(6)H(5), 4-CH(3)C(6)H(4)；ArAr = 4,4'-C(6)H(4)C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)C(6)H(3)(2-CH(3))]衍生物。这些芳基重氮基配合物5 - 8与HCl的质子化反应得到芳基重氮[MnCl(CO)(2)(ArN=NH)P(2)]（9）和[{MnCl(CO)(2)P(2)}(2)(μ-HN=NArArN=NH)]（10）衍生物。肼配合物[Mn(CO)(3)(RNHNH(2))P(2)]BPh(4)（11, 12）[P = PPh(OEt)(2), PPh(2)OEt；R = H, CH(3), C(6)H(5), 4-NO(2)C(6)H(4)]是通过先让氢化物MnH(CO)(3)P(2)与三氟甲磺酸反应，然后与适当的肼反应制备的。报道了它们通过红外光谱、(1)H和(31)P核磁共振谱以及X射线晶体结构测定的表征。化合物[Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(
