Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex†,Dalton Transactions

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Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex†
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-07-23 00:00:00 , DOI: 10.1039/c8dt02471e
Samantha L. Apps _{1,

2,

3,

4} , Andrew J. P. White _{1,

2,

3,

4} , Philip W. Miller _{1,

2,

3,

4} , Nicholas J. Long _{1,

2,

3,

4}

Affiliation

The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH₂PPh₂)₃, NP₃^Ph) are reported. Reaction of N-triphos with [MoX₃(THF)₃] (X = Cl, Br, I) gave the Mo(III) complex [MoX₃(κ²-NP₃^Ph)(THF)] (1), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N₂)(dppm)(κ³-NP₃^Ph)] (2), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)₂(dppm)(κ³-NP₃^Ph)] (4), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex 2. The reactivity of the dinitrogen complex 2 with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H⁺, BBr₃ and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to 2 resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh₂)(PCP)][B(C₆F₅)₄] (7), where PCP, [Ph₂PCNHCH₂PPh₂] is the carbenic ligand formed upon rearrangement from the reaction of 2 with M[B(C₆F₅)₄] (M = Li, Na or K). Single crystal X-ray diffraction of complexes 1, 2, 4 and 7 provided structural confirmation of the N-triphos molybdenum complexes described.

中文翻译：

N-triphos Mo（0）二氮配合物的合成和反应活性†

报道了由以氮为中心的三脚架膦配体（N-triphos，N（CH ₂ PPh ₂）₃，NP ₃^Ph）负载的新型钼二氮配合物的制备和反应活性。的N-三膦与反应[MOX ₃（THF）₃ ]（X =氯，溴，I）得到的Mo（III）配合物[MOX ₃（κ ² -NP ₃^博士）（THF）]（1），其中观察到双齿N-三磷酸配合。在DPPM（双（二苯基膦基）甲烷）的存在下该复合物还原，得到二氮络合物[沫（N ₂）（DPPM）（κ ³ -NP ₃^Ph）]（ 2），其表现出适度的二氮活化。一个额外的氢化物络合物，[沫（H）₂（DPPM）（κ³ -NP₃^博士）]（ 4），要么在还原步骤中产生的作为次要副产物，或作为通过直接氢化主要产物二氮配合物2。还研究了二氮配合物2与一系列路易斯酸的反应性。在低温下，质子或硼烷路易斯酸（H⁺，BBr₃发现三（五氟苯基）硼烷和三（五氟苯基）硼烷（BCF）与N-triphos配体的顶部氮原子配位，没有确凿的证据表明二氮配体有任何功能化。向2中添加碱金属路易斯酸会导致N-三磷酸配体的意外重排，从而形成[Mo（dppm）（PMePh ₂）（PCP）] [B（C ₆ F ₅）₄ ]（7），其中PCP， [Ph ₂ PCNHCH ₂ PPh ₂ ]是2与M [B（C ₆ F ₅）₄]（M = Li，Na或K）。复合物的单晶X射线衍射1，2，4和7提供的N-三膦钼络合物结构的确认进行说明。

更新日期：2018-07-23

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