Well‐Defined Soluble P<sup>3−</sup>‐Containing Rare‐Earth‐Metal Compounds

Lv, Yingdong; Xu, Xin; Chen, Yaofeng; Leng, Xuebing; Borzov, Maxim V.

doi:10.1002/anie.201105378

Cited by 49 publications

(30 citation statements)

References 20 publications

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“…We also find that 3 can be prepared from the cyclometallate complex 4 (ref. 65), NaPH 2 and two equivalents of 12C4 in 38% crystalline yield, reflecting the high solubility of this complex. The 31 P{ 1 H} NMR spectrum exhibits a singlet at 150.8 p.p.m., which in the 31 P NMR spectrum is a doublet ( J PH =107 Hz), confirming the presence of the phosphinidene hydrogen atom (Supplementary Figs 11 and 12); the latter resonates as a doublet at 9.4 p.p.m.…”

Section: Resultsmentioning

confidence: 97%

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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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Section: Resultsmentioning

confidence: 97%

“…For arsenic, the arsenido tetramer [U(Tren TIPS )AsK 2 ] 4 could be prepared33, but apart from cryogenic matrix isolation conditions5264 there are no reports of discrete actinide-phosphidos, in-line with the rare nature of this phosphorus trianion in the f-block65. With uranium–pnictide complexes in-hand we have endeavoured to prepare the thorium analogues.…”

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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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“…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). 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.…”

Section: P 4 Activation By Scandium Arene Complexesmentioning

confidence: 74%

“…These developments, as well as the report of transient (Thomson et al, 2010) and isolated (King et al, 2012) uranium nitride complexes, bide well for the discovery of other interesting bonding motifs with f elements. Recently, a P 3--containing rare earth complex, [K(toluene)](-I)4[Y4(THF)4(-PAr)4YI](-P) (Ar = 2,6-di-iso-Pr-C6H3), was isolated from YI2(THF)3 (P[SiMe3][Ar]) (Chart 3) (Lv et al, 2011). The list of rare earth-element multiple bonds is still missing terminal metal carbenes.…”

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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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“…[8] Phosphinidene complexes of other rare-earth metals were subsequently reported, and their phosphinidene transfer chemistry and small-molecule activation reactions described. [9][10][11][12][13][14] Despite the increased activity in rare-earth metal phosphinidene chemistry,t he area is considerably underdeveloped relative to transition metal phosphinidene chemistry. [15] At erminally bonded phosphinidene ligand remains ak ey target in rare-earth metal chemistry,a lthough auranium complex of such aligand was reported recently.…”

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Yttrium Complexes of Arsine, Arsenide, and Arsinidene Ligands

2015

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[3], in which the dianion 3 contains the first example of an arsinidene ligand in rare-earth metal chemistry.T he molecular structures of the arsine,a rsenide,a nd arsinidene complexes are described, and the yttrium-arsenic bonding is analyzed by density functional theory.Rare-earth metal compounds containing soft heteroatom donor ligands have attracted considerable interest in recent years. [1][2][3][4][5][6] Thec ombination of Lewis acidic M 3+ cations with heavy p-block donor atoms results in ah ard-soft mismatch that can lead to unusual bonding properties and to distinct reactivity.W ithin this context, rare-earth metal complexes of anionic phosphorus donor ligands such as phosphide (R 2 P À ) have been extensively studied. [7] Akey development occurred in 2008, when alutetium phosphinidene (RP 2À )complex was structurally characterized and its phosphinidene transfer reactivity towards aldehydes and ketones demonstrated. [8] Phosphinidene complexes of other rare-earth metals were subsequently reported, and their phosphinidene transfer chemistry and small-molecule activation reactions described. [9][10][11][12][13][14] Despite the increased activity in rare-earth metal phosphinidene chemistry,t he area is considerably underdeveloped relative to transition metal phosphinidene chemistry. [15] At erminally bonded phosphinidene ligand remains ak ey target in rare-earth metal chemistry,a lthough auranium complex of such aligand was reported recently. [16] Thechemistry of rare-earth metal complexes with arsenic donor ligands is almost entirely unexplored:arsenide (R 2 As À ) complexes are rare, [17][18][19][20][21][22] and arsinidene (RAs 2À )l igands are unknown in rare-earth metal chemistry.T he development of synthetic routes to rare-earth metal arsinidene complexes could lead to more novel reactivity,s uch as arsinidene transfer, and would also furnish new opportunities for using arsenic ligands to influence the electronic structure and magnetism of lanthanide(III) complexes.W ith these possibilities in mind, we now report the first example of arare-earth metal arsinidene complex.Our strategy involved the initial synthesis of ap rimary arsine complex of yttrium to establish the metal-arsenic bond, followed by deprotonation of the {YAsH 2 R} unit to give corresponding yttrium-arsenide and yttrium-arsinidene complexes.T hus,a dding one stoichiometric equivalent of mesitylarsine to Cp' 3 Yi nt oluene led to the formation of [Cp' 3 Y{As(H) 2 Mes}] (1)( Cp' = h 5 -C 5 H 4 Me,M es = mesityl), which was crystallized as colorless blocks in 88 %y ield (Scheme 1). To obtain the yttrium arsenide complex, 1 was dissolved in toluene and one equivalent of nBuLi was added. Thee nsuing work-up allowed isolation of the trimetallic m-arsenide complex [{Cp' 2 Y[m-As(H)Mes]} 3 ]·toluene (2·tolu-ene) in 59 %y ield.Deprotonation of 2 by nBuLi in thf, followed by crystallization from the same solvent, resulted in formation the heterobimetallic yttrium-lithium m-arsinidene complex [Li(thf)

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Well‐Defined Soluble P³⁻‐Containing Rare‐Earth‐Metal Compounds

Cited by 49 publications

References 20 publications

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

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

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

Yttrium Complexes of Arsine, Arsenide, and Arsinidene Ligands

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Well‐Defined Soluble P3−‐Containing Rare‐Earth‐Metal Compounds

Cited by 49 publications

References 20 publications

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

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

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

Yttrium Complexes of Arsine, Arsenide, and Arsinidene Ligands

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Product

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Well‐Defined Soluble P³⁻‐Containing Rare‐Earth‐Metal Compounds