Synthesis and Thermolysis of the Phosphorus‐Rich Manganese(I) Complex [Mn2(μ‐Br){cyclo‐(P4tBu3)PtBu}(CO)6]: From Complexes to Metal Phosphides
Synthesis and Thermolysis of the Phosphorus‐Rich Manganese(I) Complex [Mn2(μ‐Br){cyclo‐(P4tBu3)PtBu}(CO)6]: From Complexes to Metal Phosphides
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磷富锰(I)络合物[Mn2(μâBr){cycloâ(P4tBu3)PtBu}(CO)6]的合成和热解：从络合物到金属磷化物
DOI：
10.1002/cplu.201200013
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发表时间：
2012
期刊：
影响因子：
3.4
通讯作者：
E. Hey-Hawkins
中科院分区：
文献类型：
--
作者：
A. Kircali;R. Frank;S. Gómez-Ruiz;B. Kirchner;E. Hey-Hawkins
Compounds with a high phosphorus content such as cyclooligophosphanes [1, 2] and alkali metal oligophosphanides [3, 4] are highly attractive owing to their reactivity and interesting structural properties. Furthermore, the corresponding transitionmetal complexes could be suitable precursors for binary metal phosphides (MxPy with y> x or yx), which have a wide range of applications such as corrosion resistors,[5] catalysts for hydrodesulfurization and hydrodenitrogenation,[6] oxygen barriers,[7] semiconductors,[8] magnetic materials,[9] anode materials in lithium ion batteries,[10] and nanoparticles.[11] The rational synthesis of [Na (thf) 4 {cyclo-(P5tBu4)}][12] has paved the way for the synthesis of the corresponding phosphorus-rich transition-metal complexes.[13] The [cyclo-(P5tBu4)] À anion reacts in three different ways: 1) the [cyclo-(P5tBu4)] À ring is retained, as in [M-{cyclo-(P5tBu4)} 2](M= Pd, Ni),[14][Rh {cyclo-(P5tBu4)}(PPh3) 2],[15] and [Au {cyclo-(P5tBu4)}(PCyp3)],[16] 2) elimination of tBuCl occurs with formation of cyclo-(P5tBu3), for example,[Ni {cyclo-(P5tBu3)}-(PEt3) 2],[12] or 3) rearrangement to [{cyclo-(P4tBu3)} PtBu] À occurs, which exhibits different bonding modes, for example, bidentate chelating in [PtCl {cyclo-(P4tBu3) PtBu}(PMe2Ph)][14] and bridging (through the exocyclic PtBu group) in [M4-{cyclo-(P4tBu3) PtBu} 4](M= Cu, Ag, Au).[17] We have now observed a novel bonding mode in [Mn2 (μ-Br)-{cyclo-(P4tBu3) PtBu}(CO) 6](2), which was obtained by reaction of Na [cyclo-(P5tBu4)](1) with [MnBr (CO) 5](1: 2) in THF (Scheme 1). Compound 2 was also obtained when the reaction was performed in 1: 1 ratio or in a CO atmosphere. The 31P {1H} NMR spectrum of 2 (in C6D6) shows four multiplets for the ABC2D spin system at about d= 119, 25, À15, and À116ppm (ratio 1: 1: 2: 1). The chemical shifts and coupling constants [18] were calculated by using the simulation program SpinWorks 3 [19] and are in good agreement with the experimental data. Coupling with the quadrupolar nuclei 55 Mn (I= 5/2, N= 100%) results in broad multiplets for PD (À116. 9 ppm) and PC (À15. 4 ppm) bonded directly to the manganese atom. The mass spectrum of 2 (ESI) shows the molecular ion peak [M+ Na]+ and characteristic fragments.Compound 2 exhibits a distorted heterocubane-like structure with one missing edge [20] in which Mn1, Mn2, Br1, P1, P2, P3, P4, and P5 occupy the corners (Figure 1).[21] Rearrangement of the [cyclo-(P5tBu4)] À anion to [{cyclo-(P4tBu3)} PtBu] À has taken place. The phosphorus-rich anion bridges two Mn (CO) 3 moieties resulting in formation of two four-membered MP3 rings, which have the PBÀPD bond as common edge (dihedral angle Mn1P3/Mn2P3: 85.1 (2) 8). A similar bonding mode with formation of one four-membered ring is observed in [PtCl-{cyclo-(P4tBu3) PtBu}(PMe2Ph)].[14] All PÀP bond lengths (219.93 (9)–222.41 (8) pm) indicate single bonds.[22] The cyclo-(P4tBu3) ring formed by P2, P3, P4, and P5 adopts a butterfly conformation with the tBu groups in an all-trans conformation. The MnÀP bonds of the exocyclic bridging PtBu group are sim-
Compounds with a high phosphorus content such as cyclooligophosphanes [1, 2] and alkali metal oligophosphanides [3, 4] are highly attractive owing to their reactivity and interesting structural properties. Furthermore, the corresponding transitionmetal complexes could be suitable precursors for binary metal phosphides (MxPy with y> x or yx), which have a wide range of applications such as corrosion resistors,[5] catalysts for hydrodesulfurization and hydrodenitrogenation,[6] oxygen barriers,[7] semiconductors,[8] magnetic materials,[9] anode materials in lithium ion batteries,[10] and nanoparticles.[11] The rational synthesis of [Na (thf) 4 {cyclo-(P5tBu4)}][12] has paved the way for the synthesis of the corresponding phosphorus-rich transition-metal complexes.[13] The [cyclo-(P5tBu4)] À anion reacts in three different ways: 1) the [cyclo-(P5tBu4)] À ring is retained, as in [M-{cyclo-(P5tBu4)} 2](M= Pd, Ni),[14][Rh {cyclo-(P5tBu4)}(PPh3) 2],[15] and [Au {cyclo-(P5tBu4)}(PCyp3)],[16] 2) elimination of tBuCl occurs with formation of cyclo-(P5tBu3), for example,[Ni {cyclo-(P5tBu3)}-(PEt3) 2],[12] or 3) rearrangement to [{cyclo-(P4tBu3)} PtBu] À occurs, which exhibits different bonding modes, for example, bidentate chelating in [PtCl {cyclo-(P4tBu3) PtBu}(PMe2Ph)][14] and bridging (through the exocyclic PtBu group) in [M4-{cyclo-(P4tBu3) PtBu} 4](M= Cu, Ag, Au).[17] We have now observed a novel bonding mode in [Mn2 (μ-Br)-{cyclo-(P4tBu3) PtBu}(CO) 6](2), which was obtained by reaction of Na [cyclo-(P5tBu4)](1) with [MnBr (CO) 5](1: 2) in THF (Scheme 1). Compound 2 was also obtained when the reaction was performed in 1: 1 ratio or in a CO atmosphere. The 31P {1H} NMR spectrum of 2 (in C6D6) shows four multiplets for the ABC2D spin system at about d= 119, 25, À15, and À116ppm (ratio 1: 1: 2: 1). The chemical shifts and coupling constants [18] were calculated by using the simulation program SpinWorks 3 [19] and are in good agreement with the experimental data. Coupling with the quadrupolar nuclei 55 Mn (I= 5/2, N= 100%) results in broad multiplets for PD (À116. 9 ppm) and PC (À15. 4 ppm) bonded directly to the manganese atom. The mass spectrum of 2 (ESI) shows the molecular ion peak [M+ Na]+ and characteristic fragments.Compound 2 exhibits a distorted heterocubane-like structure with one missing edge [20] in which Mn1, Mn2, Br1, P1, P2, P3, P4, and P5 occupy the corners (Figure 1).[21] Rearrangement of the [cyclo-(P5tBu4)] À anion to [{cyclo-(P4tBu3)} PtBu] À has taken place. The phosphorus-rich anion bridges two Mn (CO) 3 moieties resulting in formation of two four-membered MP3 rings, which have the PBÀPD bond as common edge (dihedral angle Mn1P3/Mn2P3: 85.1 (2) 8). A similar bonding mode with formation of one four-membered ring is observed in [PtCl-{cyclo-(P4tBu3) PtBu}(PMe2Ph)].[14] All PÀP bond lengths (219.93 (9)–222.41 (8) pm) indicate single bonds.[22] The cyclo-(P4tBu3) ring formed by P2, P3, P4, and P5 adopts a butterfly conformation with the tBu groups in an all-trans conformation. The MnÀP bonds of the exocyclic bridging PtBu group are sim-
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影响因子：
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DOI：
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