[{(η5-C5Me5)2Sm}4P8]: A Molecular Polyphosphide of the Rare-Earth Elements

Konchenko, Sergey N.; Pushkarevsky, Nikolay A.; Gamer, Michael T.; Köppe, Ralf; Schnöckel, Hansgeorg; Roesky, Peter W.

doi:10.1021/ja901045m

Cited by 116 publications

(87 citation statements)

References 43 publications

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“…The average Pinner-Pcorner distance of 2.20 Å is close to the P-P interatomic distance in P4 (2.21 Å) (Corbridge and Lowe, 1952) or a recent updated gas phase value 2.1994(3) Å (Cossairt et al, 2010a). The structure of the P8 unit resembled that of (Cp*2Sm)4P8 (Konchenko et al, 2009). The P8 unit had been previously observed in some late transition metal complexes, which were obtained from the photolysis reaction of P4…”

supporting

confidence: 59%

“…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%

“…DFT calculations on model molecules of Sc 4 P 8 and Sc 3 P 7 indicated that the two polyphosphide complexes exhibit mostly ionic interactions between the metal and the polyphosphide anion as described for (Cp * 2Sm)4P8 (Konchenko et al, 2009). The examination of bonding orbitals with the same symmetry, HOMO-15 for Sc 4 P 8 and HOMO-18 for Sc 3 P 7 ( Figure 15), revealed some overlapping between the 3d orbitals of scandium and the 3p orbitals of phosphorous.…”

mentioning

confidence: 89%

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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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supporting

confidence: 59%

Section: P 4 Activation By Scandium Arene Complexesmentioning

confidence: 74%

mentioning

confidence: 89%

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

Huang

Diaconescu

2014

Including Actinides

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“…[5,6] On the contrary, early transition metal mediated P4 activation is much less investigated and rare-earth examples are rare. [7][8][9][10][11][12][13] Roesky et al reported the formation of (Cp * 2Sm)4P8 from slow vapour transfer of P4 into a toluene solution of Cp * 2Sm. [12] Our group recently reported a direct P4 activation by well defined scandium and yttrium naphthalene or anthracene complexes under ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

P₄ Activation by Lanthanum and Lutetium Naphthalene Complexes Supported by a Ferrocene Diamide Ligand

Huang

Diaconescu

2013

Eur J Inorg Chem

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Two rare‐earth (La and Lu) naphthalene complexes supported by a ferrocene diamide ligand activate P4 under ambient conditions to form M3P7 species exclusively. The resulting complexes feature a Zintl‐type polyphosphide P73– unit stabilized by three lanthanide fragments. The reported metal complexes were characterized by X‐ray crystallography, multinuclear NMR spectroscopy, and elemental analysis.

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“…[16] The structure of the complex is very rare and can be described as a realgartype P 8 4À ligand trapped in a cage of four samarocenes. As no triple-decker sandwich complex of the rare-earth elements with a polyphosphide middle-deck bridging the metal centers is known, we focused our interest on the cyclo-P 5 ligand.…”

mentioning

confidence: 99%

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block

Wiecko

Pushkarevsky

et al. 2011

Angew Chem Int Ed

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Triple-and multidecker sandwich complexes have been discussed in the last decades for their unique electrical and magnetic properties. The organic spacer between the metals may facilitate intermetallic electronic communication, which has a high potential for molecular electronics.[1] A number of one-dimensional organometallic sandwich molecular wires (SMWs) have been extensively studied. Thus, the multilayer vanadium-arene (Ar) organometallic complexes [V n (Ar) m ], which can be produced in a molecular beam by laser vaporization, are a class of one-dimensional molecular magnets.[2] Ferrocene-based molecular wires have been synthesized in the gas phase and characterized by mass spectroscopy.[3] It was calculated that these compounds have half-metallic properties with 100 % negative spin polarization near the Fermi level in the ground state.[4] In contrast to this investigation in the gas phase, studies on related organometallic triple-and multidecker sandwich complexes containing f-block elements (lanthanides or actinides) in condensed phase remain rare;[5] studies were mostly on the cyclooctatetraene ligand and its derivatives. The only rare-earth-element triple-decker complex with heterocycles is the low-valent scandium 1,3,5-triphosphabenzene complex [{(h 5 -P 3 C 2 tBu 2 )Sc} 2 (m-h 6 :h 6 -P 3 C 3 tBu 3 )], which was obtained by cocondensation of scandium vaporized in an electron beam with an excess of the phosphaalkyne tBuCP.[6] Apart from organometallic compounds, triple-and multidecker sandwich complexes of the 4f elements consisting of "salen" type Schiff base ligands, [7] phthalocyanines, and porphyrins have been extensively studied because these compounds exhibit tunable spectroscopic, electronic, and redox properties, and different extents of intramolecular p-p interactions.[8] Despite these promising physical properties further investigations on 4f elements based triple-and multidecker sandwich complexes are obviously hampered by the limited variety of ligands that have been attached to the metal centers to date. Based on these considerations, we present herein mixed d/f-block-metal triple-decker complexes with a purely inorganic all-phosphorus middle deck.In contrast to d-block chemistry, where purely inorganic ring systems of Group 15 elements such as P 5 and P 6 , [9] As 5 , [9c] and Sb 5 [10] are well-established, there is no analogy with the fblock elements to date. On the other hand, it was shown only recently that rare-earth elements can stabilize highly reactive main-group species such as N 2 3À .[11] Although some heavier Group 15-lanthanide compounds, such as phosphides (Ln À PR 2 ), [12] arsenides (Ln À AsR 2 ), [12d, 13] stibides (Ln À Sb 3 ), [14] and bismutides (LnÀBiÀBiÀLn) [15] are known, the first molecular polyphosphide of the rare-earth elements, [(Cp* 2 Sm) 4 P 8 ] (Cp* = h 5 -C 5 Me 5 ), was recently synthesized. [16] The structure of the complex is very rare and can be described as a realgartype P 8 4À ligand trapped in a cage of four samarocenes. As no triple-decker sandw...

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[{(η⁵-C₅Me₅)₂Sm}₄P₈]: A Molecular Polyphosphide of the Rare-Earth Elements

Abstract: [{(eta(5)-C(5)Me(5))(2)Sm}(4)P(8)], a molecular polyphosphide of the rare-earth elements having a realgar core structure, was synthesized by a one-electron redox reaction of divalent samarocen and white phosphorus.

Cited by 116 publications

References 43 publications

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

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

P₄ Activation by Lanthanum and Lutetium Naphthalene Complexes Supported by a Ferrocene Diamide Ligand

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block

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[{(η5-C5Me5)2Sm}4P8]: A Molecular Polyphosphide of the Rare-Earth Elements

Abstract: [{(eta(5)-C(5)Me(5))(2)Sm}(4)P(8)], a molecular polyphosphide of the rare-earth elements having a realgar core structure, was synthesized by a one-electron redox reaction of divalent samarocen and white phosphorus.

Cited by 116 publications

References 43 publications

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

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

P4 Activation by Lanthanum and Lutetium Naphthalene Complexes Supported by a Ferrocene Diamide Ligand

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P5 Building Block

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Product

Resources

About

[{(η⁵-C₅Me₅)₂Sm}₄P₈]: A Molecular Polyphosphide of the Rare-Earth Elements

P₄ Activation by Lanthanum and Lutetium Naphthalene Complexes Supported by a Ferrocene Diamide Ligand

Mixed‐Metal Lanthanide–Iron Triple‐Decker Complexes with a cyclo‐P₅ Building Block