Bicyclic P<sub>6</sub> as Complex Ligand

Scherer, Otto J.; Werner, Bernd; Heckmann, Gert; Wolmershäuser, Gotthelf

doi:10.1002/anie.199105531

Cited by 58 publications

(37 citation statements)

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“…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). All known examples of lanthanide (Chart 22) (Konchenko et al, 2009;Li et al, 2011) and actinide (Scherer et al, 1991;Stephens, 2004) mediated P4 activation had involved low-valent metal complexes prior to our reports. For example, (Cp*2Sm)4P8 was obtained by vapor transfer of P4 to a toluene solution of Cp*2Sm over the course of a week in a low yield (ca.…”

Section: P 4 Activation By Scandium Arene Complexesmentioning

confidence: 74%

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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Section: P 4 Activation By Scandium Arene Complexesmentioning

confidence: 74%

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

Huang

Diaconescu

2014

Including Actinides

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“…For example, under ambient conditions there are only a handful of each class of structurally authenticated formal Th=C carbene134445, Th=N imido464748 and terminal Th=O oxo or Th=E···K (E=O, S, Se, Te) complexes495051 known; where thorium–phosphorus multiple bonds are concerned, they are conspicuous by their absence outside of cryogenic matrix isolation experiments52. Indeed, of fewer than thirty crystallographically authenticated thorium–phosphorus complexes in the Cambridge Structural Database53 seven are phosphanides54555657585960, three are polyphosphides6162, one is a phosphinidiide54, a term we use to indicate its bridging nature, and the remainder are phosphine derivatives; a dithorium-phosphinidiide complex [{Th(η 5 -C 5 Me 5 ) 2 (OMe)} 2 (μ-PH)] (ref. 36) has been described though not structurally confirmed.…”

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confidence: 99%

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

et al. 2016

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Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated with stabilising these linkages at the large thorium ion. Here we report structurally authenticated examples of a parent thorium(IV)–phosphanide (Th–PH2), a terminal thorium(IV)–phosphinidene (Th=PH), a parent dithorium(IV)–phosphinidiide (Th–P(H)-Th) and a discrete actinide–phosphido complex under ambient conditions (Th=P=Th). Although thorium is traditionally considered to have dominant 6d-orbital contributions to its bonding, contrasting to majority 5f-orbital character for uranium, computational analyses suggests that the bonding of thorium can be more nuanced, in terms of 5f- versus 6d-orbital composition and also significant involvement of the 7s-orbital and how this affects the balance of 5f- versus 6d-orbital bonding character.

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“…41 Yet another unique P 6 ligand geometry has been provided by Wolczanski and coworkers who found that if a reaction mixture containing ( t Bu 3 SiO) 3 NbPMe 3 and P 4 was allowed to incubate at −78 • C for 7 h, followed by slow warming to 23 • C, then the red P 6 -complex, (( t Bu 3 SiO) 3 Nb) 2 (µ 2 :η 2 ,η 2 -c P 3 -c P 3 ), 51, could be isolated in 77% yield. 34 In 51, two of the niobium-phosphorus distances of 2.559 (8) 67 What distinguished the octaphosphorus cluster in 52 from other related structural motifs seen in polyphosphorus ligands derived from P 4 was the fact that it incorporated a metal-phosphinidene bond, the reactivity of which was exploited, in one instance through phospha-Wittig chemistry.…”

Section: 77%mentioning

confidence: 99%

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

2010

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Introduction 4164 2. P 4 Activation Leading to P 1 , P 2 , and P 3 Products 4165 2.1. Terminal and Bridging P 1 Ligands from P 4 4165 2.2. Bridging P 2 Ligands from P 4 4166 2.3. Cyclo-P 3 Units Derived from P 4 4168 3. P 4 Activation Leading to P 4 Products 4169 3.1. Coordination of P 4 Tetrahedra 4169 3.2. Rearranged P 4 Products 4169 4. P 4 Activation Leading to P g5 Products 4171 5. Functionalization and Transfer Methodologies 4173 5.1. Functionalization and Subsequent Reactivity of Terminal Monophosphide and Bridging Diphosphorus Complexes Derived from P 4 4173 5.2. Reactivity and Transfer Chemistry of the Cyclo-P 3 Functional Group 4174 5.3. Functionalization and Transfer Chemistry of Polyphosphorus Ligands (P g4 ) Derived from P 4 4175 6. Concluding Remarks 4175 6.1. Conclusions 4175 6.2. Future Prospects 4176 7. Acknowledgments 4176 8. References 4176

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Bicyclic P₆ as Complex Ligand

Abstract: The binuclear Th complex 1 contains a new type of P6 ligand, which is derived formally from P6 benzvalene. Amber‐colored, extremely air‐sensitive crystals of 1 are formed on cothermolysis of the butadiene complex [Cp2Th(η4‐C4H6] and P4 in toluene.

Cited by 58 publications

References 16 publications

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

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

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

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Bicyclic P6 as Complex Ligand

Abstract: The binuclear Th complex 1 contains a new type of P6 ligand, which is derived formally from P6 benzvalene. Amber‐colored, extremely air‐sensitive crystals of 1 are formed on cothermolysis of the butadiene complex [Cp2Th(η4‐C4H6] and P4 in toluene.

Cited by 58 publications

References 16 publications

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

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

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

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Bicyclic P₆ as Complex Ligand