Albertin Gabriele, Antoniutti Stefano, Bacchi Alessia, Bergamo Massimo, Bordignon Emilio, 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. 1998 Feb 9;37(3):479-489. doi: 10.1021/ic970463e.
Reaction of OsH(2)P(4) [P = P(OEt)(3), PPh(OEt)(2), PPh(2)OEt] with methyl triflate followed by the treatment with hydrazines gave the [OsH(RNHNH(2))P(4)]BPh(4) (1-3) (R = H, CH(3), C(6)H(5), 4-NO(2)C(6)H(4)) derivatives. Instead, the reaction of OsH(2)P(4) first with methyl triflate, then with triflic acid, and finally with an excess of the appropriate hydrazine afforded the bis(hydrazine) Os(RNHNH(2))(2)P(4)(2) (4, 5) (R = H, CH(3), C(6)H(5)) complexes. Also the Os(NH(2)NH(2)){P(OEt)(3)}(5)(2) (7) derivative was prepared. All the hydrazine complexes were fully characterized by IR and (1)H and (31)P NMR spectra, and a single-crystal X-ray structure determination of the complex Os(NH(2)NH(2))(2){P(OEt)(3)}(4)(2).C(2)H(5)OH (4a) is reported. The compound crystallizes in the space group P2(1)/c with a = 20.550(4) Å, b = 19.663(4) Å, c = 20.843(4) Å, beta = 99.84(9) degrees, and Z = 4. The coordination around the osmium atom is octahedral and the orientation of the ligands in the Os(NH(2)NH(2))(2){P(OEt)(3)}(4) cation is determined by several strong hydrogen bonds involving hydrazine nitrogen and phosphite oxygen atoms. Amidrazone complexes Os{eta(2)-NH=C(R1)N(R)NH(2)}{P(OEt)(3)}(4)(2) (8, 9) (R = H, CH(3); R1 = CH(3), 4-CH(3)C(6)H(4)) were prepared by allowing nitrile complexes Os(R1CN)(2)P(4)(2) to react with hydrazine NH(2)NH(2) or methylhydrazine CH(3)NHNH(2). Reaction of complexes containing substituted hydrazine ligands of the type [OsH(RNHNH(2))P(4)]BPh(4) and Os(RNHNH(2))(2)P(4)(2) [P = P(OEt)(3); R = CH(3), C(6)H(5)] with Pb(OAc)(4) at -30 degrees C results in the selective oxidation of the hydrazine affording the corresponding diazene [OsH(RN=NH)P(4)]BPh(4) (10) and Os(RN=NH)(2)P(4)(2) (11) derivatives. The first bis(methyldiazene) complex Os(CH(3)N=NH)(2){P(OEt)(3)}(4)(2) (11b) was thus prepared.
OsH(2)P(4) [P = P(OEt)(3)、PPh(OEt)(2)、PPh(2)OEt] 与三氟甲磺酸甲酯反应，随后用肼处理，得到 [OsH(RNHNH(2))P(4)]BPh(4) (1 - 3)（R = H、CH(3)、C(6)H(5)、4 - NO(2)C(6)H(4)）衍生物。相反，OsH(2)P(4) 先与三氟甲磺酸甲酯反应，再与三氟甲磺酸反应，最后与过量的合适肼反应，得到双（肼）Os(RNHNH(2))(2)P(4)(2) (4, 5)（R = H、CH(3)、C(6)H(5)）配合物。还制备了 Os(NH(2)NH(2)){P(OEt)(3)}(5)(2) (7) 衍生物。所有肼配合物均通过红外光谱、(1)H 和 (31)P NMR 光谱进行了全面表征，并报道了配合物 Os(NH(2)NH(2))(2){P(OEt)(3)}(4)(2).C(2)H(5)OH (4a) 的单晶 X 射线结构测定。该化合物结晶于空间群 P2(1)/c 中，a = 20.550(4) Å，b = 19.663(4) Å，c = 20.843(4) Å，β = 99.84(9)°，Z = 4。锇原子周围的配位为八面体，Os(NH(2)NH(2))(2){P(OEt)(3)}(4) 阳离子中配体的取向由涉及肼氮和亚磷酸酯氧原子的几个强氢键决定。通过使腈配合物 Os(R1CN)(2)P(4)(2) 与肼 NH(2)NH(2) 或甲基肼 CH(3)NHNH(2) 反应，制备了脒腙配合物 Os{η(2)-NH=C(R1)N(R)NH(2)}{P(OEt)(3)}(4)(2) (8, 9)（R = H、CH(3)；R1 = CH(3)、4 - CH(3)C(6)H(4)）。含有 [OsH(RNHNH(2))P(4)]BPh(4) 和 Os(RNHNH(2))(2)P(4)(2) 类型取代肼配体的配合物 [P = P(OEt)(3)；R = CH(3)、C(6)H(5)] 在 - 30℃下与 Pb(OAc)(4) 反应，导致肼选择性氧化，得到相应的重氮烯 [OsH(RN=NH)P(4)]BPh(4) (10) 和 Os(RN=NH)(2)P(4)(2) (11) 衍生物。由此制备了首个双（甲基重氮烯）配合物 Os(CH(3)N=NH)(2){P(OEt)(3)}(4)(2) (11b)。
