Homometallic Rare‐Earth Metal Phosphinidene Clusters: Synthesis and Reactivity

Wang, Kai; Luo, Gen; Hong, Jianquan; Zhou, Xigeng; Weng, Linhong; Luo, Yi; Zhang, Lixin

doi:10.1002/ange.201307422

Cited by 13 publications

(3 citation statements)

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“…6 However, few methods for the formation of unactivated secondary alkyl 30 trifluoromethylthioethers from unactivated alkenes have been reported. 7 One straightforward method for the formation of unactivated secondary alkyl trifluoromethylthioethers is the Markovnikovselective hydro-trifluoromethylthiolation 8 of unactivated olefins 35 since olefins are inexpensive and readily available starting materials. 9 Interestingly, anti-Markovnikov additions of thiols across alkenes, namely thio-ene reaction, have been well studied, 10 while the Markovnikov-selective hydrothiolation remains much less studied.…”

Section: Proceeds Via a Free-radical Pathwaymentioning

confidence: 99%

“…14 In both cases, the ring-closed products 6 were obtained in 70% and 50% yields, respectively. We reasoned that the alkyl radical generated from the addition of a 35 hydrogen atom to the alkene undergoes irreversible intramolecular 5-exo-cyclization at a much faster rate than those of the bimolecular radical quenching process. This experiment strongly suggests the involvement of a free-radical mechanism in the iron-mediated hydro-trifluoromethylthiolation reaction.…”

Section: Proceeds Via a Free-radical Pathwaymentioning

confidence: 99%

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Iron-mediated Markovnikov-selective hydro-trifluoromethylthiolation of unactivated alkenes

2015

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Section: Proceeds Via a Free-radical Pathwaymentioning

confidence: 99%

Section: Proceeds Via a Free-radical Pathwaymentioning

confidence: 99%

Iron-mediated Markovnikov-selective hydro-trifluoromethylthiolation of unactivated alkenes

2015

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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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confidence: 99%

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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N‐Heterocyclic Carbene–Phosphinidyne Transition Metal Complexes

Doddi¹,

Bockfeld²,

Bannenberg³

et al. 2014

Angewandte Chemie

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The N‐heterocyclic carbene–phosphinidene adduct IPrPSiMe3 is introduced as a synthon for the preparation of terminal carbene–phosphinidyne transition metal complexes of the type [(IPrP)MLn] (MLn=(η6‐p‐cymene)RuCl) and (η5‐C5Me5)RhCl). Their spectroscopic and structural characteristics, namely low‐field 31P NMR chemical shifts and short metal–phosphorus bonds, show their similarity with arylphosphinidene complexes. The formally mononegative IPrP ligand is also capable of bridging two or three metal atoms as demonstrated by the preparation of bi‐ and trimetallic RuAu, RhAu, Rh2, and Rh2Au complexes.

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Homometallic Rare‐Earth Metal Phosphinidene Clusters: Synthesis and Reactivity

Cited by 13 publications

References 59 publications

Iron-mediated Markovnikov-selective hydro-trifluoromethylthiolation of unactivated alkenes

Iron-mediated Markovnikov-selective hydro-trifluoromethylthiolation of unactivated alkenes

Yttrium Complexes of Arsine, Arsenide, and Arsinidene Ligands

N‐Heterocyclic Carbene–Phosphinidyne Transition Metal Complexes

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