Preparation of mer-[Mo(N2)3(PPr2Ph)3] from trans-[Mo(N2)2(PPr2Ph)4]; Its X-Ray Crystal Structure, Spectroscopic Properties, and Protonation to Give Ammonia.
Preparation of mer-[Mo(N2)3(PPr2Ph)3] from trans-[Mo(N2)2(PPr2Ph)4]; Its X-Ray Crystal Structure, Spectroscopic Properties, and Protonation to Give Ammonia.
复制标题
由反式-[Mo(N2)2(PPr2Ph)4]制备mer-[Mo(N2)3(PPr2Ph)3]；
DOI：
10.1002/chin.198651256
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发表时间：
1986
期刊：
影响因子：
--
通讯作者：
R. L. Richards
中科院分区：
文献类型：
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作者：
S. Anderson;D. Hughes;R. L. Richards
以[MoCl_3（thf）_3]（thf =四氢呋喃）或MoCl_5在四氢呋喃中与PPrn_2 Ph在氮气保护下经镁还原制得的化合物trans-[Mo（N_2）_2（PPrn_2 Ph）_4]（1），与氮气在苯或四氢呋喃中反应，高产率地得到mer-[Mo（N_2）_3（PPrn_2 Ph）_3]（2）。通过X-射线晶体结构测定证实了mer构型，其显示化合物具有d（Mo-N）= 2.050（9）、1.984（9）和2.015（8），d（N-N）= 1.092（10）、1.124（9）和1.103（9）π。最长的N-N和最短的Mo-N距离是唯一的N2配体。光谱（i.r.; 31 P、15 N和95 Mo n.m.r.）报道了配合物的性质。化合物（1）和（2）在甲醇中用H2SO 4质子化得到氨[对于（1）和（2）分别为0.3和1.3mol NH3/Mo原子]。讨论了化合物（2）与PEt_2Ph和PBu_3的类似物的存在。
The compound trans-[Mo(N2)2(PPrn2Ph)4](1), prepared by magnesium reduction of [MoCl3(thf)3](thf = tetrahydrofuran) or MoCl5 in thf together with PPrn2Ph under N2, reacts with N2 in benzene or thf to give mer-[Mo(N2)3(PPrn2Ph)3](2) in high yield. The mer configuration is confirmed by an X-ray crystal structure determination which shows the compound to have d(Mo–N)= 2.050(9), 1.984(9), and 2.01 5(8), d(N–N)= 1.092(10), 1.124(9), and 1.103(9)Å. The longest N–N and shortest Mo–N distances are for the unique N2 ligand. Spectroscopic (i.r.; 31P, 15N, and 95Mo n.m.r.) properties of the complexes are reported. Protonation of compounds (1) and (2) in methanol with H2SO4 gave ammonia [0.3 and 1.3 mol NH3 per Mo atom for (1) and (2) respectively]. The occurrence of analogues of compound (2) with PEt2Ph and PBu3 is discussed.