Albertin G, Antoniutti S, Bacchi A, Ballico G B, Bordignon E, Pelizzi G, Ranieri M, Ugo P
Dipartimento di Chimica, Università Ca'Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy.
Inorg Chem. 2000 Jul 24;39(15):3265-79. doi: 10.1021/ic991393+.
The mono- and binuclear aryldiazene complexes [Re(C6H5N=NH)(CO)5-nPn]BY4 (1-5) and (Re(CO)5-nPn)2-(mu-HN=NAr-ArN=NH)2 (6-12) [P = P(OEt)3, PPh(OEt)2, PPh2OEt; n = 1-4; Ar-Ar = 4,4'-C6H4-C6H4, 4,4'-(2-CH3)C6H3-C6H3(2-CH3), 4,4'-C6H4-CH2-C6H4; Y = F, Ph) were prepared by reacting the hydride species ReH(CO)5-nPn with the appropriate mono- and bis(aryldiazonium) cations. These compounds, as well as other prepared compounds, were characterized spectroscopically (IR; 1H, 31P, 13C, and 15N NMR data), and 1a was also characterized by an X-ray crystal structure determination. [Re(C6H5N=NH)(CO)(P(OEt)3)4]BPh4 (1a) crystallizes in space group P1 with a = 15.380(5) A, b = 13.037(5) A, c = 16.649(5) A, alpha = 90.33(5) degrees, beta = 91.2(1) degrees, gamma = 89.71(9) degrees, and Z = 2. The "diazene-diazonium" complexes M(CO)3P2(HN=NAr-ArN identical to N)2 (13-15, 17) [M = Re, Mn; P = PPh2OEt, PPh2OMe, PPh3; Ar-Ar = 4,4'-C6H4-C6H4, 4,4'-C6H4-CH2-C6H4] and Re(CO)4(PPh2OEt)(4,4'-HN=NC6H4-C6H4N identical to N)2 (16b) were synthesized by allowing the hydrides MH(CO)3P2 or ReH(CO)4P to react with equimolar amounts of bis(aryldiazonium) cations under appropriate conditions. Reactions of diazene-diazonium complexes 13-17 with the metal hydrides M2H2P'4 and M2'H(CO)5-nP"n afforded the heterobinuclear bis(aryldiazene) derivatives M1(CO)3P2(mu-HN=NAr-ArN=NH)M2HP'42 (ReFe, ReRu, ReOs, MnRu, MnOs) and M1(CO)3P2(mu-HN=NAr-ArN=NH)M2'(CO)5-nP"n2 (ReMn, MnRe) [M1 = Re, Mn; M2 = Fe, Ru, Os; M2' = Mn, Re; P = PPh2OEt, PPh2OMe; P',P" = P(OEt)3, PPh(OEt)2; Ar-Ar = 4,4'-C6H4-C6H4, 4,4'-C6H4-CH2-C6H4; n = 1, 2]. The heterotrinuclear complexes Re(CO)3(PPh2OEt)2(mu-4,4'-HN=NC6H4-C6H4N=NH)M(P(OEt)3)4(mu-4,4'-HN=NC6H4- C6H4N=NH)Mn(CO)3(PPh2OEt)24 (M = Ru, Os) (ReRuMn, ReOsMn) were obtained by reacting the heterobinuclear complexes ReRu and ReOs with the appropriate diazene-diazonium cations. The heterobinuclear complex with a bis(aryldiazenido) bridging ligand [Mn(CO)2(PPh2OEt)2(mu-4,4'-N2C6H4-C6H4N2)Fe(P(OEt)3)4]BPh4 (MnFe) was prepared by deprotonating the bis(aryldiazene) compound Mn(CO)3(PPh2OEt)2(mu-4,4'-HN=NC6H4-C6H4N=NH)Fe(4- CH3C6H4CN)(P(OEt)3)43. Finally, the binuclear compound Re(CO)3(PPh2OEt)2(mu-4,4'-HN=NC6H4-C6H4N2)Fe(CO)2(P(OPh)3)22 (ReFe) containing a diazene-diazenido bridging ligand was prepared by reacting [Re(CO)3(PPh2OEt)2(4,4'-HN=NC6H4-C6H4N identical to N)]+ with the FeH2(CO)2(P(OPh)3)2 hydride derivative. The electrochemical reduction of mono- and binuclear aryldiazene complexes of both rhenium (1-12) and the manganese, as well as heterobinuclear ReRu and MnRu complexes, was studied by means of cyclic voltammetry and digital simulation techniques. The electrochemical oxidation of the mono- and binuclear aryldiazenido compounds Mn(C6H5N2)(CO)2P2 and (Mn(CO)2P2)2(mu-4,4'-N2C6H4-C6H4N2) (P = PPh2OEt) was also examined. Electrochemical data show that, for binuclear compounds, the diazene bridging unit allows delocalization of electrons between the two different redox centers of the same molecule, whereas the two metal centers behave independently in the presence of the diazenido bridging unit.
单核和双核芳基二氮烯配合物[Re(C6H5N=NH)(CO)5-nPn]BY4 (1 - 5)和(Re(CO)5-nPn)2-(μ-HN=NAr-ArN=NH)2 (6 - 12) [P = P(OEt)3, PPh(OEt)2, PPh2OEt; n = 1 - 4; Ar-Ar = 4,4'-C6H4-C6H4, 4,4'-(2-CH3)C6H3-C6H3(2-CH3), 4,4'-C6H4-CH2-C6H4; Y = F, Ph]通过使氢化物物种ReH(CO)5-nPn与适当的单核和双(芳基重氮鎓)阳离子反应制备。这些化合物以及其他制备的化合物通过光谱表征(红外光谱；1H、31P、13C和15N核磁共振数据)，并且1a还通过X射线晶体结构测定进行了表征。[Re(C6H5N=NH)(CO)(P(OEt)3)4]BPh4 (1a)在空间群P1中结晶，a = 15.380(5) Å，b = 13.037(5) Å，c = 16.649(5) Å，α = 90.33(5)°，β = 91.2(1)°，γ = 89.71(9)°，Z = 2。“二氮烯 - 重氮鎓”配合物M(CO)3P2(HN=NAr-ArN≡N)2 (13 - 15, 17) [M = Re, Mn; P = PPh2OEt, PPh2OMe, PPh3; Ar-Ar = 4,4'-C6H4-C6H4, 4,4'-C6H4-CH2-C6H4]和Re(CO)4(PPh2OEt)(4,4'-HN=NC6H4-C6H4N≡N)2 (16b)通过使氢化物MH(CO)3P2或ReH(CO)4P在适当条件下与等摩尔量的双(芳基重氮鎓)阳离子反应合成。二氮烯 - 重氮鎓配合物13 - 17与金属氢化物M2H2P'4和M2'H(CO)5-nP"n的反应得到异双核双(芳基二氮烯)衍生物M1(CO)3P2(μ-HN=NAr-ArN=NH)M2HP'42 (ReFe、ReRu、ReOs、MnRu、MnOs)和M1(CO)3P2(μ-HN=NAr-ArN=NH)M2'(CO)5-nP"n2 (ReMn、MnRe) [M1 = Re, Mn; M2 = Fe, Ru, Os; M2' = Mn, Re; P = PPh2OEt, PPh2OMe; P',P" = P(OEt)3, PPh(OEt)2; Ar-Ar = 4,4'-C6H4-C6H4, 4,4'-C6H4-CH2-C6H4; n = 1, 2]。异三核配合物Re(CO)3(PPh2OEt)2(μ-4,4'-HN=NC6H4-C6H4N=NH)M(P(OEt)3)4(μ-4,4'-HN=NC6H4-C6H4N=NH)Mn(CO)3(PPh2OEt)24 (M = Ru, Os) (ReRuMn、ReOsMn)通过使异双核配合物ReRu和ReOs与适当的二氮烯 - 重氮鎓阳离子反应获得。具有双(芳基二氮烯基)桥连配体的异双核配合物[Mn(CO)2(PPh2OEt)2(μ-4,4'-N2C6H4-C6H4N2)Fe(P(OEt)3)4]BPh4 (MnFe)通过使双(芳基二氮烯)化合物Mn(CO)3(PPh2OEt)2(μ-4,4'-HN=NC6H4-C6H4N=NH)Fe(4-CH3C6H4CN)(P(OEt)3)43去质子化制备。最后，通过使[Re(CO)3(PPh2OEt)2(4,4'-HN=NC6H4-C6H4N≡N)]+与FeH2(CO)2(P(OPh)3)2氢化物衍生物反应制备了含有二氮烯 - 二氮烯基桥连配体的双核化合物Re(CO)3(PPh2OEt)2(μ-4,4'-HN=NC6H4-C6H4N2)Fe(CO)2(P(OPh)3)22 (ReFe)。通过循环伏安法和数字模拟技术研究了铼(1 - 12)和锰的单核和双核芳基二氮烯配合物以及异双核ReRu和MnRu配合物的电化学还原。还研究了单核和双核芳基二氮烯基化合物Mn(C6H5N2)(CO)2P2和(Mn(CO)2P2)2(μ-4,4'-N2C6H4-C6H4N2) (P = PPh2OEt)的电化学氧化。电化学数据表明，对于双核化合物，二氮烯桥连单元允许电子在同一分子的两个不同氧化还原中心之间离域，而在二氮烯基桥连单元存在下两个金属中心独立行为。
