Hydrazido(2–)-complexes of molybdenum and tungsten formed from dinitrogen complexes by protonation and ligand exchange
Hydrazido(2–)-complexes of molybdenum and tungsten formed from dinitrogen complexes by protonation and ligand exchange
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通过质子化和配体交换由二氮配合物形成钼和钨的肼基(2–)配合物
DOI：
10.1039/dt9780001766
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发表时间：
1978
期刊：
影响因子：
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通讯作者：
R. L. Richards
中科院分区：
文献类型：
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作者：
J. Chatt;A. J. Pearman;R. L. Richards
用浓缩氢与顺式[M(N_2)_2(P_Me_2Ph)_4]在甲醇中反应，合成了一系列新的肼(2-)配合物[MX_2(NNH_2)(PMe2Ph)_3](A；M=Mo或W，X=Cl、Br或I)和反式[MX(NNH_2)(PMe2Ph)_4]X(B；M=W)。将不同的配体L加入到配合物(A)中，得到了一系列如下类型的配合物：(B：M=Mo或W)，当L=PMe2Ph；(C)，[MX(NH2)(PMe2Ph)3L]X，当L=各种吡啶碱或二甲基甲酰胺；(D)，[M(NH2)(Quin)(PMe2Ph)3]X，当L=8-喹啉离子(Quin)时；特别是当M=W和X=Br时，[WBrNH2)(S2CNMe2)(PMe2Ph)2](L=S2CNMe2)。(B)型络合物反式[WF(NNH2)(PMe2Ph)4][BF4]是在硼硅酸盐玻璃反应罐中与氟化氢在甲醇中反应得到的。盐(E)[Wx(NNH_2)(PMe2Ph)_3L]-[BPh_4](M=W)是由Na[BPh_4]与(C；M=W)反应得到的，当[W(NNH_2)(2S-Ph)(PMe2Ph)_3][BPh_4][BPh_4]时，L=吡啶-2-硫醇(2HS-py)除外。通过反式[M(N_2)_2(Dppe)_2]与水溶液在四氢呋喃中的反应，合成了反式[MI(NNH_2)(Dppe)_2]_i(dppe=Ph2PCH_2CH_2PPh2)配合物。光谱学(IR.和n.m.r.)根据它们的结构讨论了这些络合物的数据。在二氯甲烷溶液中，络合物(A)、(C)和(D)以一个单位被电化学氧化，但不能被还原。
A number of new hydrazido(2–)-complexes [MX2(NNH2)(PMe2Ph)3](A; M = Mo or W, X = Cl, Br, or I) and trans-[MX(NNH2)(PMe2Ph)4]X (B; M = W) have been prepared by reaction of concentrated HX with cis-[M (N2)2(PMe2Ph)4] in methanol. The addition of various ligands L to complexes (A) has given a series of complexes of the following types: (B : M = Mo or W), when L = PMe2Ph; (C), [MX(NNH2)(PMe2Ph)3L]X, when L = various pyridine bases or dimethylformamide; (D), [M(NNH2)(quin)(PMe2Ph)3]X, when L = quinolin 8-olate ion (quin); and specifically [WBr(NNH2)(S2CNMe2)(PMe2Ph)2](L = S2CNMe2) when M = W and X = Br. The (B)-type complex trans-[WF(NNH2)(PMe2Ph)4][BF4] is obtained by treatment of cis-[W(N2)2-(PMe2Ph)4] with H F in methanol in a borosilicate-glass reaction vessel. The salts (E), [WX(NNH2)(PMe2Ph)3L]-[BPh4](M = W), areobtained by reaction of Na[BPh4] with (C; M = W) exceptfor L = pyridine-2-thiol (2HS-py) when [W(NNH2)(2S-py)(PMe2Ph)3][BPh4] results. The complexes trans-[MI(NNH2)(dppe)2]I (dppe = Ph2PCH2CH2PPh2) have been prepared by treatment of trans-[M(N2)2(dppe)2] with aqueous Hl in tetrahydro-furan. Spectroscopic (i.r. and n.m.r.) data for these complexes are discussed in terms of their structures. In dichloromethane solution, complexes (A), (C), and (D) are electrochemically oxidised by one unit, but cannot be reduced.