Die Stabilisierung von Tris(hydrazino)phosphan durch Komplexbildung / The Stabilisation of Tris(hydrazino)phosphane by Complex Formation

Nöth, Heinrich; Thorn, Volker

doi:10.1515/znb-1981-0601

Zeitschrift Für Naturforschung B

1981

DOI: 10.1515/znb-1981-0601

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Die Stabilisierung von Tris(hydrazino)phosphan durch Komplexbildung / The Stabilisation of Tris(hydrazino)phosphane by Complex Formation

Heinrich Nöth¹,

Volker Thorn²

Abstract: Abstract The solvolysis of (CO)5CrPCl3 with N2H4 or H2N-N(CH3)2 yields (CO)5CrP(NH-NH2)3 and (CO)5CrP[NH-N(CH3)2]3 respectively containing the hitherto unknown and unstable ligands P(NH-NH… Show more

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Syntheses, Reactivity and DFT Studies of Group 2 and Group 12 Metal Complexes of Tris(pyrazolyl)methanides Featuring “Free” Pyramidal Carbanions

Bigmore

Meyer

Krummenacher

et al. 2008

Chemistry A European J

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Reactions of HC(Me2pz)3 with Grignard reagents, dialkyl magnesium compounds and dimethylzinc are reported, together with a DFT study on some of the aspects of this chemistry. Reactions of HC(Me2pz)3 with MeMgX (X=Cl or Br) gave the half-sandwich zwitterionic compounds [Mg((Me)Tpmd)X] (X=Cl (2) or Br (3); (Me)Tpmd(-)=[C(Me2pz)3](-)). Addition of HCl to 2 gave the structurally characterised half-sandwich compound [Mg{HC(Me2pz)3}Cl2(thf)] (4). The zwitterionic sandwich compound [Mg(MeTpmd)2] (5) formed in low yields in the reaction of MeMgX with HC(Me2pz)3 but was readily prepared from HC(Me2pz)3 and either MgnBu2 or MgPh2. The structurally characterised compound 5 contains two "naked" sp3-hybridised carbanions fully separated from the dicationic metal centre. Only by using MgPh2 as starting material could the half-sandwich compound [Mg(MeTpmd)Ph(thf)] (6) be isolated. The zwitterionic sandwich compound 5 reacted with HOTf (OTf(-)=[O3SCF3](-)) to form the dication [Mg{HC(Me2pz)3}2]2+ (7(2+)), which was structurally characterised. Pulsed field gradient spin-echo (PGSE) diffusion NMR spectroscopy revealed both compounds to be intact in solution. In contrast to the magnesium counterparts, HC(Me2pz)3 reacted only slowly with ZnMe2 (and not at all with ZnPh2) to form the half-sandwich zwitterion [Zn(MeTpmd)Me] (8), which contains a cationic methylzinc moiety separated from a single sp3-hybridised carbanion. Density functional calculations on the zwitterions [M(MeTpmd)Me] and [M(MeTpmd)2] (M=Mg, Zn) revealed that the HOMO in each case is a (Me)Tpmd-based carbanion lone pair. The kappa 1C isomers of [M(MeTpmd)Me] were calculated to be considerably less stable than their kappa 3N-bound counterparts, with the largest gain in energy for Mg due to the greater ease of electron transfer from metal to the (Me)Tpmd apical carbon atom on formation of the zwitterion. Moreover, the computed M-C bond dissociation enthalpies of the kappa 1C isomers of [M(MeTpmd)Me] are considerably higher than expected by simple extrapolation from the corresponding computed H-C bond dissociation enthalpy.

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Syntheses, Reactivity and DFT Studies of Group 2 and Group 12 Metal Complexes of Tris(pyrazolyl)methanides Featuring “Free” Pyramidal Carbanions

Bigmore

Meyer

Krummenacher

et al. 2008

Chemistry A European J

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show abstract

Elements of group 5

Dove¹,

Sowerby²

1983

Coordination Chemistry Reviews

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Synthesis of fac-[(i-PrNH)3P]3Mo(CO)3: a unique tris(triaminophosphino)molybdenum tricarbonyl

Chen

Tarassoli

Allured

et al. 1986

Journal of Organometallic Chemistry

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Die Stabilisierung von Tris(hydrazino)phosphan durch Komplexbildung / The Stabilisation of Tris(hydrazino)phosphane by Complex Formation

Abstract: Abstract The solvolysis of (CO)5CrPCl3 with N2H4 or H2N-N(CH3)2 yields (CO)5CrP(NH-NH2)3 and (CO)5CrP[NH-N(CH3)2]3 respectively containing the hitherto unknown and unstable ligands P(NH-NH… Show more

Cited by 3 publications

References 0 publications

Syntheses, Reactivity and DFT Studies of Group 2 and Group 12 Metal Complexes of Tris(pyrazolyl)methanides Featuring “Free” Pyramidal Carbanions

Syntheses, Reactivity and DFT Studies of Group 2 and Group 12 Metal Complexes of Tris(pyrazolyl)methanides Featuring “Free” Pyramidal Carbanions

Elements of group 5

Synthesis of fac-[(i-PrNH)3P]3Mo(CO)3: a unique tris(triaminophosphino)molybdenum tricarbonyl

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