Activation of White Phosphorus by Reduction in the Presence of a Zirconium Diamidodiphosphine Macrocycle: Formation of a Bridging Square‐Planar <i>cyclo</i>‐P<sub>4</sub> Unit

Seidel, Wolfram W.; Summerscales, Owen T.; Patrick, Brian O.; Fryzuk, Michael D.

doi:10.1002/anie.200803739

Cited by 52 publications

(24 citation statements)

References 32 publications

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“…The P 4 core is nearly a perfect square plane with 0° P–P–P–P torsion angles, P–P–P angles of 88.86(3)° and 88.83(2)° for 1 and 2 , respectively, and almost identical P–P single bonds. The average P–P bond distances found for 1 and 2 (2.233(3) and 2.248(5) Å, respectively) compare well with those recently reported for (N 2 P 2 Zr) 2 (P 4 ) (2.240(1) Å) 8 and (DippO 3 Nb) 2 (P 4 ) (2.23(2) Å), 36 formally described as containing cyclo -P 4 4– cores. In contrast, shorter P–P distances are found in formally dianionic cyclo -P 4 2– rings in Cs or U complexes (2.14–2.17 Å, see Results and Discussion below).…”

Section: Resultssupporting

confidence: 89%

Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P₄ Inverted Sandwich Compounds

et al. 2014

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We report the synthesis and comprehensive study of the electronic structure of a unique series of dinuclear group 5 cyclo-tetraphosphide inverted sandwich complexes. White phosphorus (P4) reacts with niobium(III) and tantalum(III) β-diketiminate (BDI) tert-butylimido complexes to produce the bridging cyclo-P4 phosphide species {[(BDI)(NtBu)M]2(μ-η3:η3P4)} (1, M = Nb; 2, M = Ta) in fair yields. 1 is alternatively synthesized upon hydrogenolysis of (BDI)Nb(NtBu)Me2 in the presence of P4. The trinuclear side product {[(BDI)NbNtBu]3(μ-P12)} (3) is also identified. Protonation of 1 with [HOEt2][B(C6F5)4] does not occur at the phosphide ring but rather involves the BDI ligand to yield {[(BDI#)Nb(NtBu)]2(μ-η3:η3P4)}[B(C6F5)4]2 (4). The monocation and dication analogues {[(BDI)(NtBu)Nb]2(μ-η3:η3P4)}{B(ArF)4}n (5, n = 1; 6, n = 2) are both synthesized by oxidation of 1 with AgBArF. DFT calculations were used in combination with EPR and UV–visible spectroscopies to probe the nature of the metal–phosphorus bonding.

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Section: Resultssupporting

confidence: 89%

Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P₄ Inverted Sandwich Compounds

et al. 2014

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“…Unlike main group elements and late transition metals (Caporali et al, 2010;Scheer et al, 2010), the number of Pn-containing early transition metal complexes formed from direct P4 activation is much smaller (Chirik et al, 2002;Cossairt et al, 2010b;Hey et al, 1987;Scherer et al, 1988;Seidel et al, 2009). Among early transition metals, rare earths are more Lewis acidic, leading to a more pronounced mismatch in binding between their ions and phosphorous anions (Cui et al, 2008;Lv et al, 2011;Masuda et al, 2008).…”

Section: P 4 Activation By Scandium Arene Complexesmentioning

confidence: 99%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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“…With complexes 2 and 3 in hand, we decided to explore their reactivity toward P 4 . Recent studies have mainly focused on the activation of P 4 in the coordination sphere of coordinatively unsaturated metal fragments [42][43][44][45][46][47][48][49][50][51][52] and in the presence of organic substrates, [17][18][19] e.g. the photochemical or thermal conversion of [Cp 0 Fe(CO) 2 ] 2 in the presence of P 4 results in a surprisingly broad range of different P n -containing molecules by successive lose of coordinated CO, such as [{Cp 0 (OC) 2 Fe} 2 (m-h 1 :h 1 [53][54][55] In a more recent approach low-valent transition metallates are used for P 4 activation.…”

Section: Iron Polyhydridesmentioning

confidence: 99%

Reactivity studies on [Cp′FeI]2: From iron hydrides to P4-activation

2011

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Metathesis of [Cp 0 FeI] 2 (1) with KHBEt 3 affords the polyhydride iron complexes [Cp 0 FeH 2 ] 2 (2) and [Cp 0 2 Fe 2 H 3 ] (3). The ratio in which both 2 and 3 are obtained correlates to the applied H 2 pressure during synthesis. Complex 2 activates CH-or CD-bonds in aromatic compounds and shows slow H/D exchange in the presence of D 2 at room temperature in cyclohexane solvent. [Cp 0 FeH 2 ] 2 acts as a Cp 0 Fe (I)-synthon when reacted with white phosphorus (P 4 ) to give [Cp 0 Fe] 2 (m-P 4 ) (4) as the only P-containing product. This complex is best described as a triple-decker complex with a planar arrangement of a severely distorted kite-like cyclo-P 4 unit. This distortion persists in solution and solid state as evidenced by a small PP coupling constant in the 31 P{ 1 H} NMR spectrum and a long P-P distance of 2.53 A. Complex 4 is an isomer to the long-known [{Cp 0 Fe} 2 (m-h 4 :h 4 -P 4 )] ( 5) with a cistetraphosphabutadiene moiety and it thermally rearranges to 5, [{Cp 0 Fe} 2 (m-h 3 :h 3 -P 3 )] and [Cp 0 Fe (P 5 )]. All complexes described in this paper have been completely characterized including X-ray crystallography, variable temperature NMR studies and DFT calculations. Relaxed force constants (inverse compliance constants) are used as bond strength descriptors.

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Activation of White Phosphorus by Reduction in the Presence of a Zirconium Diamidodiphosphine Macrocycle: Formation of a Bridging Square‐Planar cyclo‐P₄ Unit

Cited by 52 publications

References 32 publications

Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P₄ Inverted Sandwich Compounds

Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P₄ Inverted Sandwich Compounds

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Reactivity studies on [Cp′FeI]2: From iron hydrides to P4-activation

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Activation of White Phosphorus by Reduction in the Presence of a Zirconium Diamidodiphosphine Macrocycle: Formation of a Bridging Square‐Planar cyclo‐P4 Unit

Cited by 52 publications

References 32 publications

Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P4 Inverted Sandwich Compounds

Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P4 Inverted Sandwich Compounds

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Reactivity studies on [Cp′FeI]2: From iron hydrides to P4-activation

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Activation of White Phosphorus by Reduction in the Presence of a Zirconium Diamidodiphosphine Macrocycle: Formation of a Bridging Square‐Planar cyclo‐P₄ Unit

Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P₄ Inverted Sandwich Compounds

Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P₄ Inverted Sandwich Compounds