Thorium Metallacycle Facilitates Catalytic Alkyne Hydrophosphination

Garner, Mary E.; Parker, Bernard F.; Hohloch, Stephan; Bergman, Robert G.; Arnold, John

doi:10.1021/jacs.7b08323

Cited by 50 publications

(44 citation statements)

References 37 publications

(50 reference statements)

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“…NMR monitoring of the decomposition showed that 1 equivalent of neopentane was released in the process and that the cyclometallated complex 5 (Scheme ), which results from the C−H bond activation of an ortho ‐methyl group in the NHC mesityl substituent in 4 , was formed quantitatively. Intramolecular C−H bond activation of alkyl and aryl ligand substituents in metal–NHC complexes has been observed previously with various metals . Intramolecular ligand C−H bond activation leading to cyclometallated species is also well documented for alkylidene, alkyl and hydride complexes of tantalum and other early TMs .…”

Section: Resultssupporting

confidence: 57%

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Srivastava

Moneuse

Petit

et al. 2018

Chemistry A European J

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The straightforward synthesis of a new unsymmetrical hydroxy-tethered N-heterocyclic carbene (NHC) ligand, HL, is presented. The free ligand exhibits an unusual OH-carbene hydrogen-bonding interaction. This OH-carbene motif was used to yield 1) the first tantalum complex displaying both a Fischer- and Schrock-type carbene ligand and 2) a unique NHC-based early/late heterobimetallic complex. More specifically, the protonolysis chemistry between the ligand's hydroxy group and imido-alkyl or alkylidene-alkyl tantalum precursor complexes yielded the rare monometallic tantalum-NHC complexes [Ta(XtBu)(L)(CH tBu) ] (X=N, CH), in which the alkoxy-carbene ligand acts as a chelate. In contrast, HL only binds to rhodium through the NHC unit in [Rh(HL)(cod)Cl] (cod=cycloocta-1,5-diene), the hydroxy pendant arm remaining unbound. This bifunctional ligand scaffold successfully promoted the assembly of rhodium/tantalum heterobimetallic complexes upon either 1) the insertion of [Rh(cod)Cl] into the Ta-NHC bond in [Ta(NtBu)(L)(CH tBu) ] or 2) protonolysis between the free hydroxy group in [Rh(HL)(cod)Cl] and one alkyl group in [Ta(NtBu)(CH tBu) ].

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Section: Resultssupporting

confidence: 57%

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Srivastava

Moneuse

Petit

et al. 2018

Chemistry A European J

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“…Thus, they are less inclined to form strong interactions with ligands bearing soft-donor atoms such as phosphorus. Therefore, the actinide-phosphido bond should, and has been demonstrated, be relatively reactive [20][21][22][23][24][25][26][27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

Thorium(IV) and Uranium(IV) Phosphaazaallenes

et al. 2019

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The synthesis of tetravalent thorium and uranium complexes with the phosphaazaallene moiety, [N(tBu)C=P(C6H5)]2−, is described. The reaction of the bis(phosphido) complexes, (C5Me5)2An[P(C6H5)(SiMe3)]2, An = Th, U, with two equivalents of tBuNC produces (C5Me5)2An(CNtBu)[η2-(N,C)-N(tBu)C=P(C6H5)] with concomitant formation of P(SiMe3)2(C6H5) via silyl migration. These complexes are characterized by NMR and IR spectroscopy, as well as structurally determined using X-ray crystallography.

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“… 26 − 31 , 62 , 74 The complexes which are intermediately formed in these catalytic cycles can often be isolated and characterized in separate stoichiometric experiments ( Figure 1 ). 28 , 31 , 61 , 62 …”

Section: Introductionmentioning

confidence: 99%

“… Selection of isolated insertion products of lanthanide and actinide phosphido complexes. 28 , 31 , 61 , 62 …”

Section: Introductionmentioning

confidence: 99%

Isocyanate Insertion into a La–P Phosphide Bond: A Versatile Route to Phosphaureate-Bridged Heterobimetallic Lanthanide–Coinage-Metal Complexes

et al. 2020

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A new route to heterobimetallic lanthanide–coinage-metal complexes is disclosed. The selective insertion of organic substrates such as phenyl iso(thio)cyanate into the La–P bond of the primary phosphido complex (PN) 2 La(PHMes) ( 1 ) (with PN – = ( N -(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide) yields the phospha(thio)ureate complexes (PN) 2 La(OC(NPh)(PHMes)) ( 2 ) and (PN) 2 La(SC(NPh)(PHMes)) ( 3 ) with retention of the P H protons. Subsequent deprotonation of the phosphaureate complex 2 with potassium hexamethyldisilazide (KHMDS, K[N(SiMe 3 ) 2 ]) leads to the polymeric complex [K{(PN) 2 La(OC(NPh)(PMes))}] n ( 4 ). Complex 4 was found to be an excellent precursor for salt metathesis reactions with copper(I) and gold(I) chlorides supported by an N-heterocyclic carbene (NHC, 5 and 6 ) or a cyclic alkyl amino carbene (CAAC, 7 and 8 ). This resulted in the unprecedented formation of heterobimetallic lanthanum–coinage-metal complexes, containing the first example of a μ,κ 2 ( O , N ):κ 1 ( P )-phosphaureate bridging ligand. For an alternative route to complex 8 a direct protonolysis protocol between a new basic gold(I) precursor, namely ( Me CAAC)Au(HMDS) , and 2 was also investigated. The complexes have been characterized by multinuclear NMR spectroscopy, IR spectroscopy, and X-ray crystallography (except for 8 ).

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Thorium Metallacycle Facilitates Catalytic Alkyne Hydrophosphination

Cited by 50 publications

References 37 publications

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Thorium(IV) and Uranium(IV) Phosphaazaallenes

Isocyanate Insertion into a La–P Phosphide Bond: A Versatile Route to Phosphaureate-Bridged Heterobimetallic Lanthanide–Coinage-Metal Complexes

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