Phosphaniminato-Komplexe von Rhenium(VII). Synthesen und Kristallstrukturen von [ReO3(NPR3)] (R = Ph, Et) sowie von [ReO(OSiMe3)3(Me3SiNPEt3)]

Schlecht, Sabine; Deubel, Dirk V.; Frenking, Gernot; Geiseler, Gertraud; Harms, Klaus; Magull, Jörg; Dehnicke, Kurt

doi:10.1002/(sici)1521-3749(199906)625:6<887::aid-zaac887>3.0.co;2-s

Cited by 12 publications

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“…Electron-rich metal ions prefer the formation of μ-N-bridged dimers or multinuclear aggregates of heterocubane (four metal atoms) or partially face-centered octahedral (six metal atoms) structures both containing μ 3 -bonded phosphoraneiminato ligands. Complexes with linear or slightly bent nitrogen-bridges between the metal and the phosphorus atoms are formed by metals in high formal oxidation states, as has been demonstrated for Os(VIII) or Re(VII) compounds …”

Section: Introductionmentioning

confidence: 67%

Rhenium(V) and Technetium(V) Complexes with Phosphoraneimine and Phosphoraneiminato Ligands

et al. 2005

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Air-stable rhenium(V) nitrido complexes are formed when [ReOCl3(PPh3)2], [NBu4][ReOCl4], or [NBu4][ReNCl4] are treated with an excess of silylated phosphoraneiminates of the composition Me3SiNPPh3 or Ph2P(NSiMe3)CH2PPh2 in CH2Cl2. Complexes of the compositions [ReNCl(Ph2PCH2PPh2NH)2]Cl (1), [ReN(OSiMe3)(Ph2PCH2PPh2NH)2]Cl (2) or [ReNCl2(PPh3)2] (3) were isolated and structurally characterized. The latter compound was also produced during a reaction of the rhenium(III) precursor [ReCl3(PPh3)2(CH3CN)] and Me3SiNPPh3. Nitrogen transfer from the phosphorus to the rhenium atoms and the formation of nitrido ligands were observed in all examples. All products of reactions with an excess of the potentially chelating phosphoraneiminate Me3SiNP(Ph2)CH2PPh2 contain neutral Ph2PCH2PPh2NH ligands. The required protons are supplied by a metal-induced decomposition of the solvent dichloromethane. The Re-N(imine) bond lengths (2.055-2.110 A) indicate single bonds, whereas the N-P bond with lengths between 1.596 A and 1.611 A reflect considerable double bond character. An oxorhenium(V) phosphoraneiminato complex, the dimeric compound [ReOCl2(mu-N-Ph2PCH2PPh2N)]2 (4), is formed during the reaction of [NBu4][ReOCl4] with an equivalent amount of Ph2P(NSiMe3)CH2PPh in dry acetonitrile. The blue neutral complex with two bridging phosphoraneiminato units is stable as a solid and in dry solvents. It decomposes in solution, when traces of water are present. The rhenium-nitrogen distances of 2.028(3) and 2.082(3) A are in the typical range of bridging phosphoraneiminates and an almost symmetric bonding mode. Technetium complexes with phosphoraneimine ligands were isolated from reactions of [NBu4][TcOCl4] with Me3SiNPPh3, and [NBu4][TcNCl4] with Me3SiNP(Ph2)CH2PPh2. Nitrogen transfer and the formation of a five-coordinate nitrido species, [TcNCl2(HNPPh3)2] (5), was observed in the case of the oxo precursor, whereas reduction of the technetium(VI) starting material and the formation of the neutral technetium(V) complex [TcNCl2(Ph2PCH2PPh2NH)] (6) or [TcNCl(Ph2PCH2PPh2NH)2]Cl (7) was observed in the latter case. Both technetium complexes are air stable and X-ray structure determinations show bonding modes of the phosphoraneimines similar to those in the rhenium complexes.

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Section: Introductionmentioning

confidence: 67%

Rhenium(V) and Technetium(V) Complexes with Phosphoraneimine and Phosphoraneiminato Ligands

et al. 2005

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“…In particular, iminophosphoranes (R 3 PNR), which make up an isoelectronic series with phosphorus ylides (R 3 PCR 2 ) and phosphine oxides (R 3 PO), have been extensively studied due to not only the basic interests in their structures and reactivity but also their availability as reagents for organic synthesis and, more recently, as precursors to inorganic polymers. , In addition, they have also been of great interest in coordination chemistry as ligands for transition metals. Iminophosphoranes bonded to a transition metal in η 1 fashion can be classified into three types: (i) N -coordinated iminophosphoranes with an N-metal dative bond, − (ii) N -metalated iminophosphoranes with an N-metal covalent bond, − and (iii) P -metalated iminophosphoranes with a P-metal covalent bond.…”

Section: Introductionmentioning

confidence: 99%

Syntheses and Crystal Structures of P-Transition-Metalated Iminophosphoranes, Cp*(CO)₂M{P(NPh)(OMe)₂} (M = Fe and Ru)

et al. 2002

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The reaction of [Cp*(CO)2Fe{P(NHPh)(OMe)2}]PF6 with NaNH2 yielded the P-iron-bonded iminophosphorane Cp*(CO)2Fe{P(NPh)(OMe)2}, with deprotonation from the NHPh group on the phosphorus. The ruthenium analogue, Cp*(CO)2Ru{P(NPh)(OMe)2}, was also prepared in a similar manner. The spectroscopic properties of the metallaiminophosphoranes are quite similar to those of their PO analogue, i.e., phosphonate complexes. The X-ray structure analyses revealed that the P−N bond in Cp*(CO)2Fe{P(NPh)(OMe)2} is comparable in length to that of the ruthenium analogue, Cp*(CO)2Ru{P(NPh)(OMe)2}, and both are considerably shorter than a P−N single bond. These observations strongly suggest that the P−N bonds in the P-metalated iminophosphoranes have substantial double-bond character. The structural features of the metallaiminophosphorane of iron resemble those of the starting cation complex, indicating that their electronic structures are basically similar. The iron-iminophosphorane is thermally stable compared with its Cp analogue, which is not stable enough to isolate, suggesting that both steric and electronic factors are responsible for the stability of the Cp* complexes.

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“…We present the first theoretical study on the addition of metal oxides to ketene. The peri-, chemo-, stereo-, and regioselectivity of the addition of OsO 4 and LReO 3 (L = O - , H 3 PN, Me, Cp) to ketene were systematically investigated using density-functional theory (DFT). We are going to rationalize the selectivity of the metalla-analogous cycloadditions by the analysis of donor−acceptor interactions in the transition states.…”

Section: Introductionmentioning

confidence: 99%

[2+2] versus [3+2] Addition of Metal Oxides Across CC Double Bonds: Toward an Understanding of the Surprising Chemo- and Periselectivity of Transition-Metal-Oxide Additions to Ketene

2001

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The peri-, chemo-, stereo-, and regioselectivity of the addition of the transition-metal oxides OsO4 and LReO3 (L = O-, H3PN, Me, Cp) to ketene were systematically investigated using density-functional methods. While metal-oxide additions to ethylene have recently been reported to follow a [3+2] mechanism only, the calculations reveal a strong influence of the metal on the periselectivity of the ketene addition: OsO4 again prefers a [3+2] pathway across the C=C moiety whereas, for the rhenium oxides LReO3, the [2+2] barriers are lowest. Furthermore, a divergent chemoselectivity arising from the ligand L was found: ReO4- and (H3PN)ReO3 add across the C=O bond while MeReO3 and CpReO3 favor the addition across the C=C moiety. The calculated energy profile for the MeReO3 additions differs from the CpReO3 energy profile by up to 45 kcal/mol due to the stereoelectronic flexibility of the Cp ligand adopting eta5, eta3, and eta1 bonding modes. The selectivity of the cycloadditions was rationalized by the analysis of donor-acceptor interactions in the transition states. In contrast, metal-oxide additions to diphenylketene probably follow a different mechanism: We give theoretical evidence for a zwitterionic intermediate that is formed by nucleophilic attack at the carbonyl moiety and undergoes a subsequent cyclization yielding the thermodynamically favored product. This two-step pathway is in agreement with the results of recent experimental work.

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Phosphaniminato-Komplexe von Rhenium(VII). Synthesen und Kristallstrukturen von [ReO3(NPR3)] (R = Ph, Et) sowie von [ReO(OSiMe3)3(Me3SiNPEt3)]

Cited by 12 publications

References 3 publications

Rhenium(V) and Technetium(V) Complexes with Phosphoraneimine and Phosphoraneiminato Ligands

Rhenium(V) and Technetium(V) Complexes with Phosphoraneimine and Phosphoraneiminato Ligands

Syntheses and Crystal Structures of P-Transition-Metalated Iminophosphoranes, Cp*(CO)₂M{P(NPh)(OMe)₂} (M = Fe and Ru)

[2+2] versus [3+2] Addition of Metal Oxides Across CC Double Bonds: Toward an Understanding of the Surprising Chemo- and Periselectivity of Transition-Metal-Oxide Additions to Ketene

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Phosphaniminato-Komplexe von Rhenium(VII). Synthesen und Kristallstrukturen von [ReO3(NPR3)] (R = Ph, Et) sowie von [ReO(OSiMe3)3(Me3SiNPEt3)]

Cited by 12 publications

References 3 publications

Rhenium(V) and Technetium(V) Complexes with Phosphoraneimine and Phosphoraneiminato Ligands

Rhenium(V) and Technetium(V) Complexes with Phosphoraneimine and Phosphoraneiminato Ligands

Syntheses and Crystal Structures of P-Transition-Metalated Iminophosphoranes, Cp*(CO)2M{P(NPh)(OMe)2} (M = Fe and Ru)

[2+2] versus [3+2] Addition of Metal Oxides Across CC Double Bonds: Toward an Understanding of the Surprising Chemo- and Periselectivity of Transition-Metal-Oxide Additions to Ketene

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Syntheses and Crystal Structures of P-Transition-Metalated Iminophosphoranes, Cp*(CO)₂M{P(NPh)(OMe)₂} (M = Fe and Ru)